Asymmetric dioxazine compounds having a triazinyl bridging group and a method of production and use thereof

ABSTRACT

An asymmetric dioxazine compound of the following formula in the free acid form, ##STR1## wherein R is hydrogen, halogen, sulfo or alkoxy, R 1 , R 2  and R 3  are each hydrogen or alkyl, X 1  and X 2  are each hydrogen, halogen, alkyl, alkoxy or phenoxy, Y is alkylene, phenylene or naphthylene, Z is --SO 2  CH═CH 2 , --SO 2  CH 2  CH 2  OSO 3  H or the like, V is hydrogen, alkyl, acyl or substituted triazinyl, and Q is halogen, alkoxy, amino or a group similar to that of ##STR2## provided that R is hydrogen, and Q is amino or a group similar to that of ##STR3## when V is substituted triazinyl, which is useful for dyeing or printing fiber materials to give dyed or printed products of a brilliant blue color superior in fastness properties, particularly those such as chlorine fastness with superior build-up property.

This application is a continuation of application Ser. No. 07/467,991,filed Jan. 22, 1990, now abandoned.

The present invention relates to fiber reactive asymmetric dioxazinecompounds, their production and their use as fiber reactive dyes. Morespecifically, the present invention relates to fiber reactive asymmetricdioxazine compounds useful for dyeing or printing hydroxyl or amidegroup-containing materials, particularly cellulose fibers, natural orsynthetic polyamide or polyurethane fibers, leathers or their mixedfibers to produce dyed or printed products having superior fastnessproperties such as light fastness, wet fastness and chlorine fastness.

Fiber reactive dioxazine compounds useful for dyeing or printing suchmaterials are known as disclosed in, for example, Published UnexaminedJapanese Patent Application Nos. 57-14654, 61-14265, 63-75066 and63-170463.

However, these known dioxazine compounds are not satisfactory in theirdye performance in properties such as, level dyeing property, build-upproperty and dyeing velocity as well as fastness properties such aschlorine fastness, and they still require improvement in such dyeperformance. Of these problems, the fastness Properties of the orprinted hydroxyl or amide group-containing materials, particularly thosesuch as chlorine fastness of the dyed or printed hydroxylgroup-containing materials, are particularly significant.

The present inventors have undertaken extensive studies to solve suchproblems and have found that a specific asymmetric dioxazine compoundcan meet such needs.

The present invention provides a dioxazine compound represented by thefollowing formula (I) in the free acid form, ##STR4## wherein R ishydrogen, halogen, sulfo or alkoxy, R₁, R₂ and R₃ independently of oneanother are each hydrogen or unsubstituted or substituted alkyl, X₁ andX₂ independently of one another are each hydrogen, halogen, alkyl,alkoxy or phenoxy, Y is unsubstituted or substituted alkylene, phenyleneor naphthylene, Z is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z' in which Z' is agroup capable of being split by the action of an alkali, V is hydrogen,unsubstituted or substituted alkyl, an acyl group of the formula (1),--W--R₄ (1) in which W is carbonyl or sulfonyl, and R₄ is unsubstitutedor substituted alkyl or phenyl, or a triazinyl group of the formula (2),##STR5## (2) in which Q₁ and Q₂ independently of one another are eachunsubstituted or substituted amino, and Q is halogen, alkoxy,unsubstituted or substituted amino or a group of the formula (3),##STR6## (3) in which R₅ is hydrogen or unsubstituted or substitutedalkyl, Y₁ is unsubstituted or substituted alkylene, phenylene ornaphthylene, and Z₁ is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z" in which Z" is agroup capable of being split by the action of an alkali, with theproviso that R is hydrogen and Q is unsubstituted or substituted aminoas defined above or a group of the formula (3), when V is a triazinylgroup of the formula (2).

The present invention also provides a process for producing thedioxazine compound represented by the formula (I), which comprisessubjected 2,4,6-trihalogeno-s-triazine to condensation reactions with anintermediate dioxazine compound represented by the following formula(II) in the free acid form, ##STR7## wherein R, R₁, R₃, V, X₁ and X₂ areas defined above, an amine compound represented by the following formula(III), ##STR8## wherein R₂, Y and Z are as defined above, and optionallya compound represented by the following formula (IV),

    H--Q'                                                      (IV)

wherein Q' has the same meanings as Q except for halogen.

The present invention further provides a process for dyeing or printinghydroxyl or amide group-containing materials, which comprises using thedioxazine compound represented by the formula (I).

The dioxazine compound of the formula (I) in accordance with the presentinvention includes those having the following formulas (I-1), (I-2),(I-3) and (I-4) in the free acid form; ##STR9## wherein R' is halogen,sulfo or alkoxy, V₁ is hydrogen, unsubstituted or substituted alkyl oran acyl group of the formula (1), and R₁, R₂, R₃, X₁, X₂, Y, Z and Q areas defined above, ##STR10## wherein Q₃ is unsubstituted or substitutedamino or a group of the formula (3), and R₁, R₂, R₃, X₁, X₂, Y, Z, Q₁and Q₂ are as defined above, ##STR11## wherein R₁, R₂, R₃, R₄, W, X₁,X₂, Y, Z and Q₃ are as defined above, and ##STR12## wherein R₆ ishydrogen or unsubstituted or substituted alkyl, and R₁, R₂, R₃, X₁, X₂,Y, Z and Q are as defined above.

With respect to the symbol R, in the above formulas, the halogenincludes fluorine, chlorine and the like, and the alkoxy includes C₁ toC₄ alkoxy such as methoxy, ethoxy and the like.

With respect to the symbols R₁, R₂, R₃, R₅ and R₆, the alkyl ispreferably one having 1 to 4 carbon atoms, which is unsubstituted orsubstituted by hydroxy, cyano, C₁ to C₄ alkoxy, halogen, carbamoyl,carboxy, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkylcarbonyloxy, sulfo orsulfamoyl. R₁, R₂, R₃, R₅ and R₆ preferably are hydrogen, methyl, ethyl,n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl,4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl,2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl,2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl,2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl,4-bromobutyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl,4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl,3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl,3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl,4-ethoxycarbonylbutyl, ethylcarbonyloxymethyl, ethylcarbonyloxymethyl,2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl,3-methylcarbonoyloxypropyl, 3-ethylcarbonyloxypropyl,4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl,2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl,2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like. Ofthese R₁ is most preferably hydrogen.

With respect to the symbol R₄, the group of --W--R₄ stands for an acylgroup including alkyl-, alkenyl- or phenyl-carbonyl groups such asacetyl, propionyl, benzoyl and the like, and alkyl-, alkenyl- orphenyl-sulfonyl groups such as methanesulfonyl, p-toluenesulfonyl andthe like. The alkyl, alkenyl and phenyl in the acyl group can besubstituted by carboxy or sulfo. Such substituted acyl groups include,for example, carboxyethylcarbonyl, carboxyvinylcarbonyl, o-, m- orp-carboxyphenylcarbonyl, o-, m- or p-sulfophenylcarbonyl and o-, m- orp-sulfophenylsulfonyl.

With respect to the symbols X₁ and X₂, the halogen includes chlorine,bromine and the like, the alkyl and alkoxy includes those having 1 to 4carbon atoms such as methyl, ethyl and the like, and methoxy, ethoxy andthe like, respectively. Of those represented by X₁ and X₂, chlorine andbromine are particularly preferred. With respect to the symbols Y andY₁, the alkylene includes --CH₂)₂, --CH₂)₃, --CH₂)₂ O--CH₂)₂ and thelike. The phenylene can be unsubstituted or substituted once or twice bymethyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro, carboxy orsulfo, and the naphthylene can be unsubstituted or substituted once bysulfo. Examples thereof are: ##STR13##

In the above formulas, the linkage marked with* bonds to the group##STR14##

With respect to the symbols Z' and Z", the group capable of being splitby the action of an alkali is well known in this art and includes, forexample, sulfuric acid ester, thiosulfuric acid ester, phosphoric acidester, acetic acid ester and other ester groups, and halogen atoms.Among the groups represented by Z and Z₁, particularly preferred are--SO₂ CH═CH₂ and --SO₂ CH₂ CH₂ OSO₃ H.

With respect to the symbol Q, the halogen includes fluorine, chlorineand bromine. Of these, preferred are fluorine and chlorine. The alkoxyincludes, for example, methoxy, ethoxy and the like The unsubstituted orsubstituted amino which is also represented by Q₁, Q₂ and Q₃ includesamino, alkylamino, N,N-dialkylamino, cycloalkylamino, aralkylamino,arylamino and N,N-disubstituted amino such as N,N-dialkylamino,N-alkyl-N-cycloalkyl and N-alkyl-N-arylamino, as well as a heterocyclicring-containing amino which heterocyclic ring may be furtheraddition-condensed with a homocyclic ring and N-heterocyclicring-constituting amino which may contain additional hetero atoms (inthe present invention, the term "N-heterocyclic ring-constituting amino"is intended to mean that the nitrogen atom of the amino is a memberforming a heterocyclic ring).

In the above definition with respect to the amino, the alkyl is straightor branched one preferably having 1 to 4 carbon atoms, and preferableexamples of the cycloalkyl, aralkyl and aryl are cyclohexyl, benzyl,phenethyl, phenyl and naphthyl, respectively. Examples of theheterocyclic ring are furan, thiophene, pyrazole, pyridine, pirimidine,quinoline, benzimidazole, benzthiazole and benzoxazole. TheN-heterocyclic ring-constituting amino is preferably a six-membered ringwhich may contain additional hetero atoms such as nitrogen, oxygen andsulphur. The above-mentioned alkyl, cycloalkyl, aralkyl, aryl,heterocyclic ring and N-heterocyclic ring may be unsubstituted orsubstituted by halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁ to C₄ alkyl, C₁ to C₄ alkoxy, acylamino, ureido, hydroxyl,carboxy, sulfomethyl and sulfo.

Preferable examples of the amino represented by Q are --NH2,methylamino, hydroxymethylamino, ethylamino, propylamino, butylamino,hexylamino, β-methoxyethylamino, β-ethoxyethylamino,γ-methoxypropylamino, N,N-dimethylamino, N,N-di-hydroxymethylamino,N,N-diethylamino, β-chloroethylamino, β-cyanoethylamino,N,N-di-β-hydroxyethylamino, β-hydroxyethylamino, γ-hydroxypropylamino,benzylamino, phenethylamino, cyclohexylamino, N-methyl-N-phenylamino,N-ethyl-N-phenylamino, N-propyl-N-phenylamino, N-butyl-N-phenylamino,N-β-cyanoethyl-N-phenylamino, N-ethyl-2-methylphenylamino,N-ethyl-4-methylphenylamino, N-ethyl-3-sulfophenylamino,N-ethyl-4-sulfophenylamino, phenylamino, toluidino, xylidino,chloroanilino, anisidino, phenetidino, 2-, 3- or 4-sulfoanilino, 2,4- or2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 3- or4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino,2-carboxyl-4-sulfophenylamino, 2-methoxy-5-sulfophenylamino,2-methyl-5-sulfophenylamino, 4-sulfonaphthyl-(1)-amino,3,6-disulfonaphthyl-(1)-amino, 3,6,8-trisulfonaphthyl-(1)-amino,4,6,8-trisulfonaphthyl-(1)-amino, 6-sulfonaphthyl-(2)-amino,4,8-disulfonaphthyl-(2)-amino, 3,6,8-trisulfonaphthyl-(2)-amino,4,6,8-trisulfonaphthyl-(2)-amino, pyridyl-(2)-amino, morpholino,piperidino, piperazino, N-β-hydroxyethyl-N-methylamino,N-ethyl-N-hydroxymethylamino, carboxymethyl amino, β-carboxyethylamino,β-sulfoethylamino, N-(β-sulfoethyl)-N-methylamino, and the like.

Among the dioxazine compounds in accordance with the present invention,preferred embodiments are those having sulfo as R' in the aforesaidformula (I-1), those having hydrogen as both R₁ and R₃ in the formulas(I-2) and (I-3), and those having sulfoalkyl as R₆ in the formula (I-4).

The dioxazine compound of the formula (I) may be in the form of a freeacid or a salt of an alkali metal or alkaline earth metal. Of thesemetal salts, preferred are sodium, potassium and lithium salts.

The dioxazine compound of the formula (I) can be produced in thefollowing manner.

The intermediate dioxazine compound of the formula (II), the amine ofthe formula (III) with or without the compound of the formula (IV) canbe subjected to condensation reactions in any order with a1,3,5-trihalogeno-s-triazine, thereby obtaining the desired dioxazinecompound of the formula (I).

Although any of the condensation reactions can be carried out underoptional reaction conditions and the order of the condensation reactionsis not limited, the first condensation can be preferably carried out ata temperature of -10° to 40° C. and at a pH ranging from 2 to 9, thesecond condensation at a temperature of 0° to 70° C. and at a pH rangingfrom 2 to 9, and the third condensation if any at a temperature of 10°to 100° C. and at a pH ranging from 2 to 7. The order of thecondensation reactions is preferably in such a manner that the compoundhaving the lowest reactivity to the 1,3,5-trihalogeno-s-triazine issubjected to the first condensation reaction.

The intermediate dioxazine compound of the formula (II) can be preparedin a conventional manner, for example, as follows.

A 1,4-benzoquinone represented by the following formula (V), ##STR15##wherein X₁ and X₂ are as defined above, and X₃ and X₄ are each halogen,can be subjected to a condensation reaction with a diaminobenzenerepresented by the following formula (VI) in the free acid form,##STR16## wherein R₁ is as defined above, and a sulfodiaminobenzenerepresented by the following formula (VII) in the free acid form,##STR17## wherein R, R₃ and V are as defined above, thereby obtaining adianilide compound represented by the following formula (VIII) in thefree acid form, ##STR18## wherein R, R₁, R₃, V, X₁ and X₂ are as definedabove. Successively, the dianilide compound can be subjected to acyclization reaction, if necessary in the presence of an oxidizingagent, thereby obtaining the desired intermediate dioxazine compound(II).

In the above manner, the diaminobenzene (VI) may be replaced by anotherdiaminobenzene represented by the following formula (IX) in the freeacid form, ##STR19## wherein R₁ is as defined above, and R₆ is alkylsuch as methyl, ethyl and propyl, to obtain a dianilide represented bythe following formula (X) in the free acid form, ##STR20## wherein R,R₁, R₃, R₆, V, X₁ and X₂ are as defined above. The dianilide can besimultaneously subjected to cyclization and dealkylation, if desired inthe presence of an oxidizing agent, thereby obtaining the desiredintermediate dioxazine compound (II).

In the case where the desired intermediate dioxazine compound (II) hasunsubstituted or substituted alkyl groups as both R₃ and V, it can beprepared also by alkylating the dianilide (VIII) or the intermediatedioxazine compound (II) which have been obtained using thesulfodiaminobenzene of the formula (VII) wherein both R₃ and V arehydrogen atoms.

In the case where the desired intermediate dioxazine compound (II) hassulfo as R, or the acyl group of the formula (I) as V it can also beprepared by sulfonating or acylating the intermediate dioxazine compound(II) having hydrogen as R or V, respectively.

In the present invention, when at least one of R₃ and V is unsubstitutedor substituted alkyl, or V is the acyl group (1), such dioxazinecompound of the formula (I) can also be produced by alkylating oracylating the intermediate dioxazine compound (II) having hydrogen as atleast one of R₃ and V, or V, respectively.

In addition, the dioxazine compound represented by the formula (I-2) canalso be produced by subjecting a 2,4,6-trihalogeno-s-triazine tocondensation reactions with an intermediate dioxazine compound which isrepresented by a formula corresponding to the formula (I), provided thatV is hydrogen and Q is replaced by Q₃, and which can be prepared in anymanner described above, and the respective amine compounds of theformulas H-Q₁ and H-Q₂ wherein Q₁ and Q₂ are as defined above, in anoptional order. In the case where Q₂ is the same as Q₃ in theirmeanings, such dioxazine compound can also be produced by reacting anintermediate tioxazine compound which is represented by a formulacorresponding to the formula (I-2), provided that Q₂ and Q₃ are eachhalogen, and which can be prepared in any manner described above, withtwo molar amounts of an amine compound represented by H-Q₃ in which Q₃is as defined above.

Further, the dioxazine compound of the formula (I-3) can also beproduced in the following manner. A 2,4,6-trihalogeno-s-triazine can besubjected to condensation reactions with the intermediate dioxazinecompound (II) wherein V is hydrogen, the amine (III) and the aminecompound of the formula H-Q₃ in which Q₃ is as defined above, in anyorder. In a course of the above condensation reaction, intermediatedioxazine compounds represented by the following formulas (II-1),(II-2), (II-3) and (II-4) in their free acid forms, ##STR21## wherein Xis halogen, X₁, X₂, R₁, R₂, R₃, Q₃, Y and Z are as defined above, can beobtained. Successively, the intermediate dioxazine compounds can besubjected to acylation in a conventional manner, and the resultingcompounds corresponding to the formulas (II-1), (II-2) and (II-3) can befurther subjected to a condensation reaction with the remaining amine oramines, whereby the desired dioxazine compound of the formula (I-3) canbe produced.

The dioxazine compound (I) in accordance with the present invention isfiber-reactive and useful for dyeing or printing hydroxylgroup-containing and amide group-containing materials. The materials arepreferably in a fibrous form including unmixed or mixed fibers.

The hydroxyl group-containing materials include natural or synthetichydroxyl group-containing materials such as cellulose fiber materials,regenerated products thereof and polyvinyl alcohol. Examples of thecellulose fiber materials are cotton and other vegetable fibers such aslinen, hemp, jute and ramie fibers. Examples of the regeneratedcellulose fibers are viscose staple and filament viscose.

The amide group-containing materials include synthetic or naturalpolyamide and polyurethane. Examples of the materials, particularly inthe fibrous forms, are wool and other animal furs, silk, leather,polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The dyeing may be carried out in a suitable manner, which can beselected from conventional manners depending on the physical andchemical properties of said fiber materials.

For example, cellulose fiber materials can be dyed using the presentcompound by an exhaustion dyeing, padding including cold batch-up dyeingor printing method.

The exhaustion dyeing can be carried out at a relatively low temperaturein the presence of an acid binding agent such as sodium carbonate,trisodium carbonate, trisodium phosphate, sodium hydroxide and the like,if desired using a neutral salt such as sodium sulfate, sodium chlorideand the like, optionally together with dissolving assistants, penetrantsor level dyeing agents. The neutral salt which can be used for promotingexhaustion of the dye may be added to a dye bath at the time when a bathtemperature reaches a level desired for the dyeing or prior thereto.Alternatively the neutral salt may be added thereto dividedly.

The padding can be carried out by padding the fiber materials at ambienttemperature or an elevated temperature, and after drying, steaming ordry-heating the materials to perform the dye-fixation.

The printing can be carried out in a one-phase or two-phase manner. Theone-phase printing may be conducted by printing the fiber materials witha printing paste containing an acid binding agent such as sodiumhydrogen carobnate and the like, followed by steaming at a temperatureof 100° to 160° C. The two-phase printing may be conducted by printingthe fiber materials with a neutral or weakly acidic printing paste, andpassing the materials through a hot alkaline bath containing anelectrolyte or over-padding the materials with an alkaline paddingliquor containing an electrolyte, followed by a steaming or dry-heatingtreatment.

For the preparation of the printing paste, a paste or emulsifier such assodium alginate, starch ether and the like may be used, if desired,together with a conventional auxiliary agent such as urea and/ordispersing agent.

The acid binding agent useful for fixing the compound of the presentinvention on the cellulose fiber materials includes water-soluble basicsalts consisting of alkali or alkaline earth metals and inorganic ororganic acids or compounds capable of liberating alkalis under heatingconditions. Preferred are alkali metal hydroxides and alkali metal saltsof inorganic or organic acids having a weak or medium strength.Particularly preferred are sodium salts and potassium salts. Examplesthereof are sodium hydroxide, potassium hydroxide, sodiumhydrogencarbonate, sodium carbonate, sodium formate, potassiumcarbonate, sodium dihydrogenphosphate, disodium hydrogenphosphate,trisodium phosphate, sodium silicate, sodium trichloroacetate and thelike.

The dyeing of natural or synthetic polyamide and polyurethane fibermaterials can be carried out by performing exhaustion in an acid or weakacid bath, while controlling the pH value, and making the bath neutral,or in some cases alkaline, to perform the fixation. The dyeingtemperature ranges usually from 60° to 120° C. In order to achieve alevel dyeing, there may be used a conventional level dyeing agent suchas a condensation product of cyanuric chloride and 3 times by mole ofaminobenzenesulfonic acid or aminonaphthalenesulfonic acid, or anaddition product of stearylamine and ethylene oxide, and the like.

The present dioxazine compound (I) can be characterized by excellent dyeperformances in the dyeing and printing of fiber materials, particularlycellulose fiber materials. For example, the compound can give a dyed orprinted product excellent in light fastness, perspiration-lightfastness, wet fastness such as washing resistance, peroxide-washingresistance, perspiration resistance and acid-hydrolysis resistance, andalkali fastness, chlorine fastness, abrasion fastness and iron fastness.

The dioxazine compound (I) can also exhibit excellent build-up,level-dyeing and wash off properties and high solubility as well as highexhaustion and fixation percentages. Moreover, the dioxazine compound(I) is hardly affected by changes in dyeing temperature and dyeing bathratio, so that a dyed product with a constant quality can be obtainedwith superior reproducibility.

Moreover, the dioxazine compound (I) is characterized in properties suchit is hard to change the quality of compound even when brought intocontact with a basic substance during storage, and products dyed orprinted with the compound (I) are hard to change in their color evenwhen they are subjected to fix treatment or resin-finishing.

The present invention is illustrated in more detail with reference tothe following Examples, which are only illustrative, and in which partsand % are by weight.

EXAMPLE 1

1,4-Phenylenediamine-2,6-disulfonic acid (26.8 parts) and1,4-phenylenediamine-2-sulfonic acid (18.8 parts) were dissolved inwater (500 parts), and chloranil (24.6 parts) was added thereto. Themixture was adjusted to a pH from 4 to 8 at ambient temperature andstirred to complete the reaction. Thereafter, the reaction mixture wassalted out, and the crystals produced were isolated and dried to obtaina dianilide represented by the following formula in the free acid form.##STR22##

The dianilide (62.9 parts) was added to oleum of 10 to 30% strength(1500 parts) at a temperature of 0° to 15° C., and the mixture wasstirred at 15° to 40° C. to complete the reaction. The reaction mixturewas poured into ice water to produce crystals, which were then separatedby filtration. The cake was mixed with water, and the mixture wasadjusted to a pH ranging from 3 to 6 using an aqueous sodium hydroxidesolution and salted out using sodium chloride. The crystals wereisolated on a filter to obtain a first intermediate dioxazine compoundrepresented by the following formula in the free acid form. ##STR23##

The intermediate dioxazine compound (62.5 parts) was dissolved in water(1500 parts), and cyanuric chloride (18.5 parts) was added thereto at atemperature of 5° to 30° C. The mixture was stirred to complete thereaction, while controlling the pH within a range of 2 to 7 using anaqueous sodium carbonate solution. Sulfanilic acid (17.3 parts) wasadded thereto, and the mixture was stirred at 30° to 50° C. within thepH range of 2 to 7. The reaction mixture was salted out using sodiumchloride, and the crystals were separated to obtain a secondintermediate dioxazine compound represented by the following formula inthe free acid form. ##STR24##

The above intermediate dioxazine compound (909.8 parts) was dissolved inwater, and 1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) was addedthereto. The mixture was heated to 50° to 70° C., while controlling thepH within a range of 2 to 5, and stirring was continued under theconditions described above to complete the reaction. Potassium chloridewas added to the reaction mixture which was allowed to cool at ambienttemperature, and the crystals produced were separated on a filter toobtain an asymmetric dioxazine compound represented by the followingformula in the free acid form. ##STR25##

EXAMPLE 2

Example 1 was repeated, except that bromanil was used in place ofchloranil in an equimolar amount, thereby obtaining a dianilide, firstand second intermediate dioxazine compounds and finally a desiredasymmetric dioxazine compound in this order, the anilide having thefollowing formula in the free acid form, ##STR26## the firstintermediate dioxazine compound having the following formula in the freeacid form, ##STR27## the second intermediate dioxazine compound havingthe following formula, ##STR28## and the asymmetric dioxazine compoundhaving the following formula in the free acid form. ##STR29##

DYEING EXAMPLE 1

The asymmetric dioxazine compounds obtained in Examples 1 and 2 (each of0.1, 0.3 and 0.6 parts) were dissolved in water (200 parts) to prepareeach dye bath. Sodium sulfate (10 parts) and cotton (10 parts) wereadded to the baths, which were then heated to 60° C. Sodium carbonate (4parts) was added thereto, and dyeing was continued for 1 hour at 60° C.Thereafter, the cotton taken out was washed with water, soaped, againwashed with water and then dried to obtain each dyed product of a bluecolor superior in fastness properties, particularly those such aschlorine fastness. The build-up properties were also found to besuperior.

EXAMPLES 3 TO 50

Example 1 was repeated, except that the1,4-phenylenediamine-2,6-disulfonic acid used in Example 1 was replacedby a phenylenediamine as shown in the following table to obtain acorresponding first intermediate dioxazine compound as shown in thetable, and the 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 1was replaced by an amine compound also as shown in the table, therebyobtaining a corresponding asymmetric dioxazine compound. The colorobtained by dyeing cotton in a manner similar to that of Dyeing Example1 using each asymmetric dioxazine compound is as shown in the followingtable.

    TABLE       Phenylene- First intermediate   Example No. diamine dioxazine compound     Amine compound Color      3                         ##STR30##      ##STR31##      ##STR32##      Reddish blue      4 " "                         ##STR33##      "      5 " "                         ##STR34##      "      6 " "                         ##STR35##      "      7                         ##STR36##      ##STR37##      ##STR38##      Reddish blue      8 " "                         ##STR39##      "      9 " "                         ##STR40##      "      10 " "                         ##STR41##      "      11 " "                         ##STR42##      "      12                         ##STR43##      ##STR44##      ##STR45##      Reddish blue      13 " "                         ##STR46##      "      14 " "                         ##STR47##      "      15 " "                         ##STR48##      "  16 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4Cl "      17                         ##STR49##      ##STR50##      H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Reddish     blue  18 " " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "      19                         ##STR51##      ##STR52##      ##STR53##      Reddish blue      20 " "                         ##STR54##      "      21 " "                         ##STR55##      "      22                         ##STR56##      ##STR57##      ##STR58##      Reddish blue      23 " "                         ##STR59##      "      24 " "                         ##STR60##      "      25 " "                         ##STR61##      "      26 " "                         ##STR62##      "      27                         ##STR63##      ##STR64##      ##STR65##      Reddish blue      28 " "                         ##STR66##      "      29 " "                         ##STR67##      "      30 " "                         ##STR68##      "      31 " "                         ##STR69##      "      32                         ##STR70##      ##STR71##      H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 Cl     Reddish blue  33 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 " 34 " " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "      35                         ##STR72##      ##STR73##      ##STR74##      Reddish blue      36 " "                         ##STR75##      "      37                         ##STR76##      ##STR77##      ##STR78##      Reddish blue      38 " "                         ##STR79##      "      39 " "                         ##STR80##      "      40 " "                         ##STR81##      "      41 " "                         ##STR82##      "      42                         ##STR83##      ##STR84##      ##STR85##      Reddish blue      43 " "                         ##STR86##      "      44 " "                         ##STR87##      "      45 " "                         ##STR88##      "       46 " "                         ##STR89##      "      47                         ##STR90##      ##STR91##      ##STR92##      Reddish blue  48 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4     SO.sub.2 C.sub.2H.sub.4 Cl " 49 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2     H.sub.4 SO.sub.2 CH CH.sub.2 " 50 " " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2     H.sub.4 SO.sub.2      CHCH.sub.2 "

EXAMPLE 51

Example 1 was repeated, except that the sulfanilic acid used in Example1 was replaced by compounds as described below, thereby obtaining thecorresponding asymmetric dioxazine compounds.

(1) Orthanilic acid

(2) Methanilic acid

(3) 1-Aminonaphthalene-3,6-disulfonic acid

(4) 1-Aminonaphthalene-4,6,8-trisulfonic acid

(5) 2-Aminonaphthalene-4,8-disulfonic acid

(6) 2-Aminonaphthalene-3,6,8-trisulfonic acid

(7) Aniline-2,5-disulfonic acid

(8) Aniline

(9) m-Toluidine

(10) o-Anisidine

(11) Ammonia

(12) Ethylamine

(13) Ethanolamine

(14) β-Alanine

(15) Taurine

(16) N-Methyltaurine

EXAMPLE 52

Each of Examples 3 to 50 was repeated, except that the sulfanilic acidwas replaced by amine compounds (1) to (16) respectively in Example 51,thereby obtaining the corresponding asymmetric dioxazine compounds.

DYEING EXAMPLE 2

The asymmetric dioxazine compounds obtained in Examples 3 to 52 (each of0.1, 0.3 and 0.6 parts) were dissolved respectively in water (200 parts)to prepare each dye bath. Sodium sulfate (10 parts) and cotton (10parts) were added thereto. The baths were heated to 60° C., and thensodium carbonate (4 parts) was added thereto. Dyeing was continued for 1hour at 60° C. Thereafter, the cotton taken out was washed with water,soaped, again washed with water and then dried to obtain dyed productsof a blue color superior in fastness properties, particularly those suchas chlorine fastness. The build-up properties were also found to besuperior.

EXAMPLE 53

Example 1 was repeated, except that the sulfanilic acid and1-aminobenzene-3-β-sulfatoethylsulfone to be subjected to thecondensation reaction were exchanged in the reaction order. The sameasymmetric dioxazine compound as in Example 1 was obtained.

EXAMPLE 54

Aniline-2,5-disulfonic acid (25.3 parts) was dissolved in water (250parts), with sodium carbonate added to perform neutralization. To thissolution was added cyanuric chloride (18.5 parts) at 5° to 30° C., andthe mixture was stirred at that temperature to complete the reaction.The first intermediate dioxazine compound (62.5 parts) which had beenprepared in the same manner as in Example 1, was added to the abovereaction mixture. The resulting mixture was allowed to react, withsodium carbonate being added to neutralize the hydrochloric acidproduced, thereby obtaining the second intermediate dioxazine compoundcorresponding to that in Example 51 (7).

A mixture of the intermediate dioxazine compound obtained above and1-aminobenzene-3-β-sulfatoethylsulfone (23.1 parts) was heated to 50° to70° C., while the pH was controlled within a range of 2 to 5, and themixture was stirred to complete the reaction. Salting out usingpotassium chloride and the isolation of the crystals produced gave adesired asymmetric dioxazine compound represented by the followingformula in the free acid form. ##STR93##

The dioxazine compound was found to be the same as that obtained inExample 51 (7).

EXAMPLES 55 TO 69

Example 1 was repeated to obtain intermediate dioxazine compounds whichare as shown in the following table and which correspond to the firstintermediate dioxazine compound in Example 1, except that the1,4-phenylenediamine-2,6-disulfonic acid used in Example 1 was replacedby a phenylenediamine as shown in the table. Using the intermediatedioxazine compound, any of the procedures described in Examples 1, 53and 54 was carried out to obtain a corresponding asymmetric dioxazinecompound, except that the sulfanilic acid used in Examples 1 and 53 andaniline-2,5-disulfonic acid used in Example 54 were replaced by acompound (IV) and a phenylenediamine as shown in the table, respectivelyand the 1-aminobenzene-3-β-sulfatoethylsulfone was replaced by an aminecompound as shown in the following table.

    TABLE      Example     Color on No. Phenylenediamine Intermediate dioxazine     compound Compound (IV) Amine compound cotton             55      ##STR94##      ##STR95##      ##STR96##      ##STR97##      Reddish blue      56 " " "                         ##STR98##      "  57 " " NH(C.sub.2 H.sub.4      OH).sub.2                         ##STR99##      "      58 " "                         ##STR100##      ##STR101##      "      59                         ##STR102##      ##STR103##      ##STR104##      H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl     Reddish blue      60                         ##STR105##      ##STR106##      ##STR107##      ##STR108##      "      61 " " "                         ##STR109##      "  62 " " NH(C.sub.2 H.sub.4      OH).sub.2                         ##STR110##      "      63                         ##STR111##      ##STR112##      ##STR113##      ##STR114##      Reddish blue  64 "  " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4     SO.sub.2 C.sub.2 H.sub.4 Cl "      65                         ##STR115##      ##STR116##      ##STR117##      ##STR118##      "      66 " " "                         ##STR119##      "      67                         ##STR120##      ##STR121##      HN(C.sub.2 H.sub.4      OH).sub.2                         ##STR122##      Reddish blue      68 " "                         ##STR123##      ##STR124##      "  69 " " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.     2 H.sub.4      Cl "

DYEING EXAMPLE 3

Each of the asymmetric dioxazine compounds obtained in Examples 54 to 69(each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200 parts),and sodium sulfate (10 parts) and cotton (10 parts) were added thereto.The baths were heated to 60° C. and then sodium carbonate (4 parts) wasadded thereto. Thereafter, dyeing was continued for 1 hour 60° C. Thecotton taken out was washed with water, soaped, again washed with waterand then dried to obtain dyed products of a blue color superior infastness properties, particularly those such as chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 70

2-Methoxy-4,6-dichloro-s-triazine (18 parts) and the same intermediatedioxazine compound (62.5 parts) as that in Example 1 were subjected to acondensation reaction with each other at 30° to 50° C. within a pH of 2to 7, followed by a condensation reaction with1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts). Thereaftersalting-out gave an asymmetric dioxazine compound represented by thefollowing formula in the free acid form. ##STR125##

EXAMPLES 71-97

Example 70 was repeated to obtain a desired asymmetric dioxazinecompound, except that the intermediate dioxazine compound,2-methoxy-4,6-dichloro-s-triazine and1-aminobenzene-3-β-sulfatoethylsulfone used in Example 70 were replacedby an intermediate dioxazine compound, a dichlorotriazine and an aminecompound as shown in the following table, respectively.

    TABLE           Example No. Intermediate dioxazine compound      ##STR126##      Amine compound Color on cotton            71      ##STR127##      OCH.sub.3      ##STR128##      Reddish blue      72 " "                         ##STR129##      "      73 " "                         ##STR130##      "      74                         ##STR131##      OC.sub.2      H.sub.5                         ##STR132##      Reddish blue      75 " OCH.sub.3                         ##STR133##      "      76 " "                         ##STR134##      "  77 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl " 78 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "      79                         ##STR135##      OCH.sub.3 H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2      CHCH.sub.2 Reddish blue      80                         ##STR136##      "      ##STR137##      "      81 " "                         ##STR138##      "      82 " "                         ##STR139##      "      83                         ##STR140##      OC.sub.2      H.sub.5                         ##STR141##      Reddish blue      84 " OCH.sub.3                         ##STR142##      "      85 " "                         ##STR143##      "  86 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl " 87 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "      88                         ##STR144##      OCH.sub.3 H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2      CHCH.sub.2 Reddish blue      89                         ##STR145##      "      ##STR146##      "      90 " "                         ##STR147##      "      91 " "                         ##STR148##      "  92 " OC.sub.2      H.sub.5                         ##STR149##      "      93                         ##STR150##      OCH.sub.3      ##STR151##      Reddish blue      94 " "                         ##STR152##      "  95 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl " 96 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 " 97 " " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "

DYEING EXAMPLE 4

Each of the asymmetric dioxazine compounds obtained in Examples 70 to 97(each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200 parts),and sodium sulfate (10 parts) and cotton (10 parts) were added thereto.The baths were heated to 60° C. and then sodium carbonate (4 parts) wasadded thereto. Thereafter, dyeing was continued for 1 hour at 60° C. Thecotton taken out was washed with water, soaped, again washed with waterand then dried to obtain dyed products of a blue color superior infastness properties, particularly chlorine fastness. The dioxazinecompounds were also found to be superior in build-up properties.

EXAMPLE 98

To an aqueous solution containing the same second intermediate dioxazinecompound as in Example 1 was added diethylsulfuric acid, and the mixturewas stirred at 50° to 90° C. within a pH range of 6 to 9, therebyobtaining an intermediate dioxazine compound represented by thefollowing formula in the free acid form. ##STR153##

A mixture of the above intermediate dioxazine compound and1-aminobenzene-3-β-sulfatoethylsulfone in water was stirred at 50° to70° C. within a pH range of 2 to 5 to complete the reaction. Thereafter,salting-out using sodium chloride and the isolation of the crystalsproduced gave an asymmetric dioxazine compound represented by thefollowing formula in the free acid form. ##STR154##

EXAMPLE 99

In a manner similar to that of Example 98, each intermediate dioxazinecompound which had been obtained in the manner described in Example 51was used to obtain a corresponding asymmetric dioxazine compound.

DYEING EXAMPLE 5

Each of the asymmetric dioxazine compounds obtained in Examples 98 and99 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200 parts),and sodium sulfate (10 parts) and cotton (10 parts) were added thereto.The bath were heated to 60° C. and then sodium carbonate (4 parts) wasadded thereto. Thereafter, dyeing was continued for 1 hour at thattemperature. The cotton taken out was washed with water, soaped, againwashed with water and then dried to obtain dyed products of a blue colorsuperior in fastness properties, particularly chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 100

The second intermediate dioxazine compound obtained in Example 1 wasdissolved in water, and an excess amount of acetic anhydride was addedthereto. The mixture was allowed to react at 30° to 70° C., therebyobtaining an intermediate dioxazine represented by the following formulain the free acid form. ##STR155##

The intermediate dioxazine and 1-aminobenzene-3-β-sulfatoethylsulfone inan amount equimolar to the intermediate dioxazine were added to water,and allowed to react at 50° to 70° C. and pH 2 to 5, while beingstirred. Thereafter, salting out of the reaction mixture with sodiumchloride and the isolation of the crystals produced gave an asymmetricdioxazine compound represented by the following formula in the free acidform. ##STR156##

EXAMPLE 101

Using each of the intermediate dioxazine compounds obtained in Example51, Example 100 was repeated to obtain the corresponding asymmetricdioxazine compounds.

DYEING EXAMPLE 6

Each of the asymmetric dioxazine compounds obtained in Examples 100 and101 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water add then dried to obtain dyed products of a blue colorsuperior in fastness properties, particularly chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 102

The first intermediate dioxazine compound obtained in Example 1 (62.5parts) was dissolved in water (1500 parts), and cyanuric chloride (13.5parts) was added thereto at 5° to 30° C. The mixture was stirred tocomplete the reaction, while keeping the pH within a range of 2 to 7using sodium carbonate. Successively,1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) was added thereto.The mixture was stirred at 10° to 50° C., while keeping the pH within arange of 2 to 6, thereby obtaining an asymmetric dioxazine compoundrepresented by the following formula in the free acid form. ##STR157##

EXAMPLES 103 TO 150

Using the phenylenediamines as shown in the following table, Example 1was repeated to obtain intermediate dioxazine compounds corresponding tothe first intermediate dioxazine compound in Example 1. The intermediatedioxazine compounds obtained were allowed to react with cyanuricchloride (18.5 parts). Using the resulting second intermediate dioxazinecompound, Example 102 was repeated, except that the1-aminobenzene-3-β-sulfatoethylsulfone was replaced by an amine as shownin the following table, thereby obtaining corresponding asymmetricdioxazine compounds.

    TABLE       Phenylene- First intermediate   Example No. diamine dioxazine compound     Amine Color on cotton            103      ##STR158##      ##STR159##      ##STR160##      Reddish blue      104 " "                         ##STR161##      "      105 " "                         ##STR162##      "      106 " "                         ##STR163##      "      107                         ##STR164##      ##STR165##      ##STR166##      Reddish blue      108 " "                         ##STR167##       "      109 " "                         ##STR168##      "      110 " "                         ##STR169##      "      111 " "                         ##STR170##      "      112                         ##STR171##      ##STR172##      ##STR173##      Reddish blue      113 " "                         ##STR174##      "      114 " "                         ##STR175##      "      115 " "                         ##STR176##      "  116 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4Cl "      117                         ##STR177##      ##STR178##      H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Reddish     blue  118 " " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "      119                         ##STR179##      ##STR180##      ##STR181##      "      120 " "                         ##STR182##      "      121 " "                         ##STR183##      "      122                         ##STR184##      ##STR185##      ##STR186##      Reddish blue      123 " "                         ##STR187##      "      124 " "                         ##STR188##      "      125 " "                         ##STR189##      "      126 " "                         ##STR190##      "      127                         ##STR191##      ##STR192##      ##STR193##      Reddish blue      128 " "                         ##STR194##      "      129 " "                         ##STR195##      "      130 " "                         ##STR196##      "      131 " "                         ##STR197##      "      132                         ##STR198##      ##STR199##      H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2C.sub.2 H.sub.4 Cl     Reddish blue  133 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4     SO.sub.2 CHCH.sub.2 " 134 " " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4     SO.sub.2 CHCH.sub.2 "      135                         ##STR200##      ##STR201##      ##STR202##      "      136 " "                         ##STR203##      "      137                         ##STR204##      ##STR205##      ##STR206##      Reddish blue      138 " "                         ##STR207##      "      139 " "                         ##STR208##      "      140 " "                         ##STR209##      "      141 " "                         ##STR210##      "      142                         ##STR211##      ##STR212##      ##STR213##      Reddish blue      143 " "                         ##STR214##      "      144 " "                         ##STR215##      "      145 " "                         ##STR216##      "      146 " "                         ##STR217##      "      147                         ##STR218##      ##STR219##      ##STR220##      Reddish blue  148 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4     SO.sub.2 C.sub.2H.sub.4 Cl " 149 " " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2     H.sub.4 SO.sub.2 CHCH.sub.2 " 150 " " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2     H.sub.4 SO.sub.2      CHCH.sub.2 "

DYEING EXAMPLE 7

Each of the asymmetric dioxazine compounds obtained in Examples 102 to150 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour atthat temperature. The cotton taken out was washed with water, soaped,again washed with water and then dried to obtain dyed products of a bluecolor superior in fastness properties, particularly chlorine fastness.The dioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 151

To the reaction mixture containing the asymmetric dioxazine compoundwhich had been obtained in the same manner as in Example 102, sulfanilicacid (17.3 parts) was added. The mixture was stirred to complete thereaction at 50° to 70° C., while keeping the pH within a range of 2 to5, thereby obtaining the same asymmetric dioxazine compound as inExample 1.

Similarly, the asymmetric dioxazine compounds obtained in Examples 103to 150 were treated to obtain the same asymmetric dioxazine compounds asthose in Examples 3 to 50, respectively.

EXAMPLE 152

A asymmetric dioxazine compound (101.8 parts) which had been obtained inthe same manner as in Example 102 was dissolved in water (1500 parts),and 1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) was addedthereto. The mixture was stirred at 40° to 90° C., while keeping the PHwithin a range of 2 to 6 using aqueous sodium carbonate solution,thereby obtaining an asymmetric dioxazine compound represented by thefollowing formula in the free acid form. ##STR221##

EXAMPLE 153

Using the asymmetric dioxazine compounds obtained in Examples 103 to150, Example 152 was repeated, except that the amines described belowwere used in place of the 1-aminobenzene-3-β-sulfatoethylsulfone used inExample 52 in an amount equimolar thereto, thereby obtainingcorresponding asymmetric dioxazine compounds. ##STR222##

DYEING EXAMPLE 8

Each of the asymmetric dioxazine compounds obtained in Examples 152 and153 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a blue colorsuperior in fastness properties, particularly chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 154

An intermediate dioxazine compound (54.6 parts) represented by thefollowing formula, ##STR223## was added to 5 to 23% oleum (1000 parts),and the mixture was stirred at 80° to 100° C. The reaction mixture waspoured into ice water to produce crystals, which were then separated ona filter. The cake obtained was mixed with water and adjusted to pH 2 to7 using aqueous sodium hydroxide solution. Cyanuric chloride (18.5parts) was added thereto at 5° to 30° C., and the mixture was stirred tocomplete the reaction, while keeping the pH within a range of 2 to 7using aqueous sodium carbonate solution. Sulfanilic acid (17.3 parts)was then added thereto, and the mixture was stirred to complete thereaction at 30° to 50° C. and a pH 2 to 7. To this reaction mixture wasadded 1-aminobenzene-4-β-sulfatoethylsulfone (28.1 parts), and themixture was heated to 50° to 70° C., while keeping the pH within a rangeof 2 to 5, and stirred to complete the reaction under these conditions.The reaction mixture was allowed to cool to ambient temperature and thenmixed with potassium chloride. The isolation of the crystals producedgave a desired product, which was found to be a mixture of theasymmetric dioxazine compound obtained in Example 3 and the asymmetricdioxazine compound obtained in Example 19.

DYEING EXAMPLE 9

Using the same asymmetric dioxazine compounds as used in Dyeing Examples1 to 8, color pastes having the following composition were prepared.

    ______________________________________                                        Asymmetric dioxazine compound                                                                           5 parts                                             Urea                      5 parts                                             Sodium alginate (5%) stock paste                                                                       50 parts                                             Hot water                25 parts                                             Sodium hydrogencarbonate  2 parts                                             Balance (water)          13 parts                                             ______________________________________                                    

Mercerized cotton broad cloths were printed with the color pastes havingthe above composition, predried and steamed at 100° C. for 5 minutes.The treated cloths were washed with hot water, soaped, again washed withhot water and then dried. Thus, there were obtained printed products ofa blue color excellent in fastness properties, particularly chlorinefastness.

EXAMPLE 155

A dioxazine compound (55 parts) having the following formula in the freeacid form, ##STR224## and cyanuric chloride (18 parts) were added towater (1500 parts), and the mixture was stirred to complete the reactionat 0° to 30° C., while keeping the pH within a range of 5 to 8 usingsodium carbonate. To the reaction mixture was added taurine (13 parts),and the mixture was stirred to complete the reaction at 10° to 50° C.,while keeping the pH within a range of 4 to 7. Additional taurine (13parts) was then added thereto, and the mixture was stirred to completethe reaction at 30° to 80° C. and pH 4 to 7, thereby obtaining anintermediate dioxazine compound represented by the following formula inthe free acid form. ##STR225##

A mixture of the intermediate dioxazine compound (87 parts) and cyanuricchlorine (18 parts) in water (1500 parts) was stirred to complete thereaction at 0° C. to 30° C., while keeping the pH within a range of 5 to8 using sodium carbonate. To the reaction mixture was added taurine (13parts), and the mixture was stirred to complete the reaction at 10° to50° C. and at pH 4 to 7. 1-aminobenzene-3-β-sulfatoethylsulfone (28parts) was then added thereto, and the mixture was stirred to completethe reaction at 30° to 80° C. and at pH 4 to 7, thereby obtaining anasymmetric dioxazine compound of the following formula in the free acidform. ##STR226##

EXAMPLE 156

Example 155 was repeated, except that a dioxazine compound of thefollowing formula in the free acid form, ##STR227## was used in place ofthe starting dioxazine compound used in Example 155 in an amountequimolar thereto, thereby obtaining an asymmetric dioxazine compound ofthe following formula in the free acid form. ##STR228##

EXAMPLE 157

A mixture of a dioxazine compound (55 parts) of the following formula inthe free acid form, ##STR229## and cyanuric chloride (18 parts) in water(1500 parts) was stirred to complete the reaction at 0° to 30° C., whilecontrolling the pH within a range of 5 to 8. To the reaction mixture wasadded sulfanilic acid (17 parts), and the mixture was stirred tocomplete the reaction at 10° to 50° C. and at pH 4 to 7. Thereafter,methanilic acid (17 parts) was added thereto, and the mixture wasstirred to complete the reaction at 30° to 80° C. and at pH 4 to 7,thereby obtaining an intermediate dioxazine compound.

Using the intermediate dioxazine compound, the procedure correspondingto Example 155 was repeated to obtain an asymmetric dioxazine compoundof the following formula in the free acid form. ##STR230##

EXAMPLE 158

Each of the asymmetric dioxazine compounds obtained in Examples 155 to157 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a reddish bluecolor superior in fastness properties, particularly chlorine fastness.The dioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 159

Example 155 was repeated, except that the amines described below wereused in place of the 1-aminobenzene-3-β-sulfatoethylsulfone in an amountequimolar thereto, thereby obtaining respective corresponding asymmetricdioxazine compounds. ##STR231##

EXAMPLE 160

Example 155 was repeated, except that the amine compounds describedbelow were used in place of the taurine used in Example 155 in an amountequimolar thereto, thereby obtaining respective corresponding asymmetricdioxazine compounds.

(1) N-Methyltaurine

(2) β-Alanine

(3) Ethanolamine

(4) Diethanolamine

(5) Ethylamine

(6) Ammonia

(7) Sulfanilic acid

(8) Methanilic acid

(9) Orthanilic acid

(10) Aniline

(11) Aniline-2,5-disulfonic acid

(12) 2-Aminonaphthalene-3,6,8-trisulfonic acid

(13) 1-Aminonaphthalene-3,6-disulfonic acid

EXAMPLE 161

Example 160 was repeated, except that amines (1) to (16) described inExample 159 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 160, therebyobtaining corresponding asymmetric dioxazine compounds.

EXAMPLE 162

Each of the asymmetric dioxazine compounds obtained in Examples 159 to161 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a reddish bluecolor superior in fastness properties, particularly chlorine fastness.The dioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 163

Example 155 was repeated, except that the reaction order of the1-aminobenzene-3-β-sulfatoethylsulfone and taurine was exchanged,thereby obtaining the same asymmetric dioxazine compound as in Example155.

EXAMPLE 164

A mixture of a dioxazine compound (55 parts) having the followingformula in the free acid form, ##STR232## and cyanuric chloride (18parts) in water (1500 parts) was stirred to complete the reaction at 0°to 30° C., while keeping the pH within a range of 5 to 8 using sodiumcarbonate. To the reaction mixture was added taurine (13 parts), and themixture was stirred to complete the reaction at 10° to 50° C. and a pHranging from 4 to 7. 1-aminobenzene-3-β-sulfatoethylsulfone (28 parts)was then added to the reaction mixture, and the resulting mixture wasstirred to complete the reaction at 30° to 80° C. and a pH ranging from4 to 7, thereby obtaining an intermediate dioxazine compound of thefollowing formula in the free acid form. ##STR233##

In the above procedure, the reaction order of the1-aminobenzene-3-β-sulfatoethylsulfone and taurine was also exchangedsame intermediate dioxazine compound as above was obtained.

A mixture of the intermediate obtained above (103 parts) and cyanuricchloride (18 parts) in water (1500 parts) was stirred to complete thereaction at 0° to 30° C., while keeping the pH within a range of 5 to 8.To the reaction mixture was added taurine (13 parts), and the mixturewas stirred to complete the reaction at 10° to 50° C. and a pH rangingfrom 4 to 7. Taurine (13 parts) was additionally added thereto, and themixture was stirred to complete the reaction at 30° to 80° C. and a pHranging from 4 to 7, thereby obtaining the same asymmetric dioxazinecompound as in Example 155.

EXAMPLE 165

A mixture of a dioxazine compound (55 parts) having the followingformula in the free acid form, ##STR234## and cyanuric chloride (18parts) in water (1500 parts) was stirred to complete the reaction at 0°to 30° C., while keeping the pH within a range of 5 to 8. To thereaction mixture was added taurine (13 parts) and the mixture wasstirred to complete the reaction at 10° to 50° C. and a pH ranging from4 to 7. Thereafter, cyanuric chloride (18 parts) was added thereto, andthe mixture was stirred to complete the reaction at 0° to 30° C. and apH ranging from 5 to 8. Further, 1-aminobenzene-3-β-sulfatoethylsulfone(28 parts) was added thereto, and the mixture was stirred to completethe reaction at 10° to 50° C. and a pH ranging from 4 to 7, therebyobtaining an intermediate dioxazine compound of the following formula inthe free acid form. ##STR235##

The above procedure was repeated, except that the reaction order of the1-aminobenzene-3-β-sulfatoethylsulfone and taurine was exchanged,thereby also obtaining the same intermediate dioxazine compound asabove.

A mixture of the intermediate (118 parts) obtained above and taurine (26parts) in water (1500 parts) was stirred to complete the reaction at 30°to 80° C. and pH ranging from 4 to 7, thereby obtaining a compound,which was found to be the same as the asymmetric dioxazine compoundobtained in Example 155.

EXAMPLE 166

Example 155 was repeated, except that1-N-ethylaminobenzene-3-β-sulfatoethylsulfone was used in place of thetaurine used in Example 155 in an amount equimolar thereto, therebyobtaining an asymmetric dioxazine compound of the following formula inthe free acid form. ##STR236##

EXAMPLE 167

Example 155 was repeated, except that the amines described below wereused in place of the taurine used in Example 155 in amounts equimolarthereto, obtaining corresponding asymmetric dioxazine compounds.##STR237##

EXAMPLE 168

Example 159 was repeated, except that the amines (1) to (8) described inExample 167 were used in place of the taurine used in Example 159 inamounts equimolar thereto, thereby obtaining corresponding asymmetricdioxazine compounds.

EXAMPLE 169

Each of the asymmetric dioxazine compounds obtained in Examples 166 to168 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a reddish bluecolor superior in fastness properties, particularly chlorine fastness.The dioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 170

Using the asymmetric dioxazine compounds used in Examples 158, 162 and169, color pastes having the following composition were prepared.

    ______________________________________                                        Asymmetric dioxazine compound                                                                           5 parts                                             Urea                      5 parts                                             Sodium alginate (5%) stock paste                                                                       50 parts                                             Hot water                25 parts                                             Sodium hydrogencarbonate  2 parts                                             Balance (water)          13 parts                                             ______________________________________                                    

Mercerized cotton broad cloths were printed with the color pastes havingthe above composition, pre-dried and steamed at 100° C. for 5 minutes.The treated cloths were washed with hot water, soaped, again washed withhot water and then dried. Thus, printed products of a blue colorexcellent in fastness properties, particularly chlorine fastness wereobtained.

EXAMPLE 171

A mixture of an intermediate dioxazine compound (59 parts) having thefollowing formula in the free acid form, ##STR238## and cyanuricchloride (18 parts) in water (1500 parts) was stirred to complete thereaction at 0° to 30° C., while keeping the pH within a range of 5 to 8.Sulfanilic acid (17 parts) was added thereto, and the mixture wasstirred to complete the reaction at 10° to 50° C. and a pH ranging from5 to 8. Further, 1-aminobenzene-3-β-sulfatoethylsulfone (28 parts) wasadded thereto, and the mixture was stirred to complete the reaction at30° to 80° C. and a pH ranging from 3 to 6, thereby obtaining a desiredasymmetric dioxazine compound of the following formula in the free acidform. ##STR239##

The above intermediate dioxazine compound had been prepared by stirringa mixture of a dioxazine compound (55 parts) of the following formula inthe free acid form, ##STR240## and acetic anhydride (10 parts) in water(500 parts) at 10° to 50° C. and a pH ranging from 2 to 7.

EXAMPLE 172

Example 171 was repeated, except that an intermediate dioxazine compoundof the following formula in the free acid form, ##STR241## was used inplace of the intermediate dioxazine compound used in Example 171 in anamount equimolar thereto, thereby obtaining an asymmetric dioxazinecompound of the following formula in the free acid form, ##STR242##

The above intermediate dioxazine compound had been prepared in the samemanner as in Example 171 except that a dioxazine compound of thefollowing formula in the free acid form, ##STR243## in place of thedioxazine compound used was used in Example 171 in an amount equimolarthereto.

EXAMPLE 173

Each of the asymmetric dioxazine compounds obtained in Examples 171 and172 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a reddish bluecolor superior in fastness properties, particularly chlorine fastness.The dioxazine compounds were also found to be superior in build-upproperties.

EXAMPLES 174 TO 285

Example 171 was repeated, except that the intermediate dioxazinecompounds and amines as described in the following table were used inplace of the intermediate dioxazine compound and1-aminobenzene-3-β-sulfatoethylsulfone used in Example 171,respectively, in respective amounts equimolar thereto, thereby obtainingcorresponding asymmetric dioxazine compounds.

    TABLE       Intermediate   Example No. dioxazine compound Amine Color on cotton           174      ##STR244##      ##STR245##      Reddish blue      175 "     ##STR246##      "      176 "     ##STR247##      "      177 "     ##STR248##      "      178     ##STR249##      ##STR250##      Reddish blue      179 "     ##STR251##      "      180 "     ##STR252##      "      181 "     ##STR253##      "      182 "     ##STR254##      "      183     ##STR255##      ##STR256##      Reddish blue      184 "     ##STR257##      "      185 "     ##STR258##      "      186 "     ##STR259##       "  187 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl "      188     ##STR260##      H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Reddish     blue  189 " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2      CHCH.sub.2 "      190     ##STR261##      ##STR262##      "      191 "     ##STR263##      "      192 "     ##STR264##      "      193     ##STR265##      ##STR266##      Reddish blue      194 "     ##STR267##      "      195 "     ##STR268##      "      196 "     ##STR269##      "      197     ##STR270##      ##STR271##      Reddish blue      198 "     ##STR272##      "      199 "     ##STR273##      "      200 "     ##STR274##      "      201 "     ##STR275##      "      202     ##STR276##      ##STR277##      Reddish blue  203 " H.sub.2 N(CH.sub.2).sub.2 OC.sub. 2 H.sub.4     SO.sub.2 C.sub.2 H.sub.4 Cl " 204 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2     H.sub.4 SO.sub.2 CHCH.sub.2 " 205 " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2     H.sub.4 SO.sub.2 CHCH.sub.2 "      206     ##STR278##      ##STR279##      "      207     ##STR280##      ##STR281##      Reddish blue      208 "     ##STR282##      "      209 "     ##STR283##      "      210 "     ##STR284##      "      211     ##STR285##      ##STR286##      Reddish blue      212 "     ##STR287##      "      213 "     ##STR288##      "      214 "     ##STR289##      "      215 "     ##STR290##      "      216     ##STR291##      ##STR292##      Reddish blue      217 "     ##STR293##      "      218 "     ##STR294##      "  219 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl " 220 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2   C     CHH.sub.2 "      221     ##STR295##      H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2 Reddish     blue      222     ##STR296##      ##STR297##      "      223 "     ##STR298##      "      224 "     ##STR299##      "      225     ##STR300##      ##STR301##      Reddish blue      226 "     ##STR302##      "      227 "     ##STR303##      "      228 "     ##STR304##      "      229     ##STR305##      ##STR306##      Reddish blue      230 "     ##STR307##      "      231 "     ##STR308##      "      232 "     ##STR309##      "      233 "     ##STR310##      "      234     ##STR311##      ##STR312##      Reddish blue  235 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2     C.sub.2 H.sub.4 Cl " 236 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4     SO.sub.2 CHCH.sub.2 " 237 " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4     SO.sub.2 CHCH.sub.2 "      238     ##STR313##      ##STR314##      "      239     ##STR315##      ##STR316##      Reddish blue      240 "     ##STR317##      "      241 "     ##STR318##      "      242 "     ##STR319##      "      243     ##STR320##      ##STR321##      Reddish blue      244 "     ##STR322##      "       245 "     ##STR323##      "      246 "     ##STR324##      "      247 "     ##STR325##      "      248     ##STR326##      ##STR327##      Reddish blue      249 "     ##STR328##      "      250 "     ##STR329##      "  251 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl " 252 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2   C     CHH.sub.2 " 253 " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "      254     ##STR330##      ##STR331##      Reddish blue      255 "     ##STR332##      "      256 "     ##STR333##      "      257 "     ##STR334##      "      258 "     ##STR335##      "      259     ##STR336##      ##STR337##      Reddish blue      260 "     ##STR338##      "      261 "     ##STR339##      "      262 "     ##STR340##      "      263 "     ##STR341##      "      264     ##STR342##      ##STR343##      Reddish blue      265 "     ##STR344##      "      266 "     ##STR345##      "  267 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl " 268 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2   C     CHH.sub.2 " 269 " H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2     CHCH.sub.2 "      270     ##STR346##      ##STR347##      Reddish blue      271 "     ##STR348##      "      272 "     ##STR349##      "      273 "     ##STR350##      "      274 "     ##STR351##      "      275     ##STR352##      ##STR353##      Reddish blue      276 "     ##STR354##      "      277 "     ##STR355##      "      278 "     ##STR356##      "      279 "     ##STR357##      "      280     ##STR358##      ##STR359##      Reddish blue      281 "     ##STR360##      "      282 "     ##STR361##      "  283 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2     H.sub.4 Cl " 284 " H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2   C     CHH.sub.2 " 285 " H.sub.2 N(CH.sub. 2).sub.3 OC.sub.2 H.sub.4 SO.sub.2   C     CHH.sub.2 "

EXAMPLE 286

Example 171 was repeated, except that an intermediate dioxazine compoundof the following formula in the free acid form, ##STR362## wherein x isa sulfonation degree of about 1.2, was used in place of the intermediatedioxazine compound used in Example 171 in an amount equimolar thereto,thereby obtaining an asymmetric dioxazine compound of the followingformula in the free acid form, ##STR363## wherein x is as defined above.

The above intermediate dioxazine compound had been prepared by addingthe same intermediate dioxazine compound (65 parts) used in Example 206to 5 to 30% oleum (500 parts), stirring the mixture to complete thereaction at 20° to 70° C., pouring the reaction mixture into ice waterand then salting it out.

EXAMPLES 287 TO 302

Example 286 was repeated, except that amines described in the followingtable were used in place of the 1-aminobenzene-3-β-sulfatoethylsulfoneused in Example 286 in amounts equimolar thereto, thereby obtainingcorresponding asymmetric dioxazine compounds.

                  TABLE                                                           ______________________________________                                        Example                         Color on                                      No.    Amine                    cotton                                        ______________________________________                                        287                                                                                   ##STR364##              Reddish blue                                  288                                                                                   ##STR365##              Reddish blue                                  289                                                                                   ##STR366##              Reddish blue                                  290                                                                                   ##STR367##              Reddish blue                                  291                                                                                   ##STR368##              Reddish blue                                  292                                                                                   ##STR369##              Reddish blue                                  293                                                                                   ##STR370##              Reddish blue                                  294                                                                                   ##STR371##              Reddish blue                                  295                                                                                   ##STR372##              Reddish blue                                  296                                                                                   ##STR373##              Reddish blue                                  297                                                                                   ##STR374##              Reddish blue                                  298                                                                                   ##STR375##              Reddish blue                                  299                                                                                   ##STR376##              Reddish blue                                  300    H.sub. 2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2                  H.sub.4 Cl               Reddish                                                                       blue                                          301    H.sub.2 N(CH.sub.2).sub.2 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                         Reddish                                                                       blue                                          302    H.sub.2 N(CH.sub.2).sub.3 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                         Reddish                                                                       blue                                          ______________________________________                                    

EXAMPLE 303

Example 171 was repeated, except that the amine compounds describedbelow were used in place of the sulfanilic acid used in Example 171 ineach amounts equimolar thereto, thereby obtaining the correspondingasymmetric dioxazine compounds.

(1) Orthanilic acid

(2) Methanilic acid

(3) 1-Aminonaphthalene-3,6-disulfonic acid

(4) 1-Aminonaphthalene-4,6,8-trisulfonic acid

(5) 2-Aminonaphthalene-4,8-disulfonic acid

(6) 2-Aminonaphthalene-3,6,8-trisulfonic acid

(7) Aniline-2,5-disulfonic acid

(8) Aniline

(9) m-Toluidine

(10) o-Anisidine

(11) Ammonia

(12) Ethylamine

(13) Ethanolamine

(14) β-Alanine

(15) Taurine

(16) N-Methyltaurine

EXAMPLE 304

Examples 174 to 302 were repeated, except that amine compounds (1) to(16) described in Example 303 were used in place of sulfanilic acid,thereby obtaining the corresponding asymmetric dioxazine compounds.

EXAMPLE 305

Each of the assymetric dioxazine compounds obtained in Examples 174 to302 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a reddish bluecolor superior in fastness properties, particularly chlorine fastness.The dioxazine compounds were also found to be superior in build-upproperty.

EXAMPLE 306

Example 171 was repeated, except that the reaction order of the1-aminobenzene-3-β-sulfatoethylsulfone and sulfanilic acid wasexchanged. The same asymmetric dioxazine compound as obtained in Example171 was obtained.

EXAMPLE 307

A mixture of a dioxazine compound (55 parts) having the followingformula in the free acid form, ##STR377## and cyanuric chloride (18parts) in water (1500 parts) was stirred to complete the reaction at 0°to 30° C., while keeping the pH within a range of 5 to 8 using sodiumcarbonate. To the reaction mixture was added sulfanilic acid (17 parts),and the mixture was stirred to complete the reaction at 10° to 50° C.and a pH ranging from 5 to 8. Then, acetic anhydride (10 parts) wasadded thereto, and the mixture was stirred to complete the reaction at10° to 50° C. and pH ranging from 2 to 7.Aminobenzene-3-β-sulfatoethylsulfone (28 parts) was then added thereto,and the mixture was further stirred to complete the reaction at 30° to80° C. and a pH ranging from 3 to 6, thereby obtaining a compound, whichwas found to be the same as the asymmetric dioxazine compound obtainedin Example 171.

EXAMPLE 308

Example 307 was repeated, except that the reaction order of the1-aminobenzene-3-β-sulfatoethylsulfone and sulfanilic acid wasexchanged. The same asymmetric dioxazine compound as in Example 307 wasobtained.

EXAMPLE 309

A mixture of a dioxazine compound (55 parts) having the followingformula in the free acid form, ##STR378## and cyanuric chloride (18parts) in water (1500 parts) was stirred to complete the reaction at 0°to 30° C., while keeping the pH within a range of 5 to 8 using sodiumcarbonate. To the reaction mixture was added sulfanilic acid (17 parts),and the mixture was stirred to complete the reaction at 10° to 50° C.and a pH ranging from 5 to 8. 1-aminobenzene-3-β-sulfatoethylsulfone (28parts) was then added thereto, and the mixture was stirred to completethe reaction at 30° to 80° C. and a pH ranging from 3 to 6. Further,acetic anhydride (10 parts) was added to the reaction mixture, and themixture was stirred to complete the reaction at 10° to 50° C. and a pHranging from 2 to 7, thereby obtaining a compound which was found to bethe same as the asymmetric dioxazine compound obtained in Example 171.

EXAMPLE 310

Example 309 was repeated, except that the reaction order of the1-aminobenzene-3-β-sulfatoethylsulfone and sulfanilic acid wasexchanged, thereby obtained the same compound as obtained in Example309.

EXAMPLE 311

Aniline-2,5-disulfonic acid (25.3 parts) was added to water (1500 parts)with neutralization using sodium carbonate to obtain a clear solution.Cyanuric chloride (18 parts) was added to the clear solution at 5° to30° C., and the mixture was stirred to complete the reaction. Anintermediate dioxazine compound (59 parts) which had been obtained inthe same manner as in Example 171 was added to the above reactionmixture, and the mixture was stirred to complete the reaction, whileneutralizing the hydrochloric acid produced with sodium carbonate.Further, 1-aminobenzene-3-β-sulfatoethylsulfone (28 parts) was addedthereto, and the mixture was heated to 50° to 70° C., while keeping thepH within a range of 2 to 5, and stirred to complete the reaction,thereby obtaining a product which was found to be the same asymmetricdioxazine compound as obtained in Example 303(7).

EXAMPLE 312

A intermediate dioxazine compound (59 parts) which had been prepared asin Example 171 was dissolved in water (1500 parts), and cyanuricchloride (18 parts) was added thereto at 5° to 30° C. The mixture wasstirred to complete the reaction, while keeping the pH within a range of2 to 7 using sodium carbonate. 1-aminobenzene-3-β-sulfatoethylsulfone(28 parts) was then added thereto, and the mixture was stirred tocomplete the reaction at 10° to 50° C. and a pH ranging from 2 to 6. Tothe reaction mixture was added1-N-ethylaminobenzene-3-β-sulfatoethylsulfone (31 parts), and themixture was stirred to complete the reaction at 40° to 90° C., whilekeeping the pH within a range of 2 to 6, thereby obtaining an asymmetricdioxazine compound of the following formula in the free acid form.##STR379##

EXAMPLE 313

Example 312 was repeated, except that the amines described below wereused in place of the 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone usedin Example 312 in amounts equimolar thereto, thereby obtaining thecorresponding asymmetric dioxazine compounds. ##STR380##

EXAMPLE 314

Example 312 was repeated, except that the intermediate dioxazinecompounds described in Examples 179 to 302 were used in place of thatused in Example 312 in amounts equimolar thereto, thereby obtainingcorresponding asymmetric dioxazine compounds.

EXAMPLE 315

Example 314 was repeated, except that amines (1) to (8) described inExample 313 were used in place of the1-N-ethylaminobenzene-3-β-sulfatoethylsulfone used in Example 314 inamounts equimolar thereto, thereby obtaining corresponding asymmetricdioxazine compounds.

EXAMPLE 316

Each of the asymmetric dioxazine compounds obtained Examples 312 to 315(each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200 parts),and sodium sulfate (10 parts) and cotton (10 parts) were added thereto.The baths were heated to 60° C. and then sodium carbonate (4 parts) wasadded thereto. Thereafter, dyeing was continued for 1 hour at 60° C. Thecotton taken out was washed with water, soaped, again washed with waterand then dried to obtain dyed products of a blue color superior infastness properties, particularly chlorine fastness. The dioxazinecompounds were also found to be superior in build-up properties.

EXAMPLE 317

Using each of the asymmetric dioxazine compounds used in Examples 173,305 and 316, color pastes of the composition described below wereprepared.

    ______________________________________                                        Asymmetric dioxazine compound                                                                           5 parts                                             Urea                      5 parts                                             Sodium alginate (5%) stock paste                                                                       50 parts                                             Hot water                25 parts                                             Sodium hydrogencarbonate  2 parts                                             Balance (water)          13 parts                                             ______________________________________                                    

Mercerized cotton broad cloths were printed with the color pastes havingthe above composition, prepdried and steamed at 100° C. for 5 minutes.The treated cloths were washed with hot water, soaped, again washed withhot water and then dried. Thus, there were obtained printed products ofa blue color excellent in fastness properties, particularly chlorinefastness.

EXAMPLE 318

A mixture of a dioxazine compound (54.5 parts) having the followingformula in the free acid form, ##STR381## and cyanuric chloride (18.5parts) in water (1500 parts) was stirred to complete the reaction at 5°to 30° C., while keeping the pH within a range of 3 to 7 using aqueoussodium carbonate solution. Thereafter, sodium chloride was added to thereaction mixture, and the crystals produced were separated on a filter.The cake was dissolved in water (1500 parts), and sulfanilic acid (17.3parts) was added thereto. The mixture was stirred to complete thereaction at 30° to 50° C., while maintaining the pH within a range of 6to 9. Sodium chloride was added thereto, and crystals produced wereseparated on a filter to obtain an intermediate dioxazine compound ofthe following formula in the free acid form. ##STR382##

The intermediate dioxazine compound (83 parts) was dissolved in water(1000 parts), and 1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts)was added thereto. The mixture was stirred to complete the reaction at50° to 80° C., while maintaining the pH within a range of 2 to 5.Thereafter, potassium chloride was added thereto and then crystalsproduced were separated on a filter to obtain an asymmetric dioxazinecompound of the following formula in the free acid form. ##STR383##

EXAMPLE 319

Example 318 was repeated, except that the amine compounds describedbelow were used in place of the sulfanilic acid used in Example 318 inamounts equimolar thereto, thereby obtaining the correspondingasymmetric dioxazine compounds.

(1) Orthanilic acid

(2) Methanilic acid

(3) 1-Aminonaphthalene-3,6-disulfonic acid

(4) 1-Aminonaphthalene-4,6,8-trisulfonic acid

(5) 2-Aminonaphthalene-4,8-disulfonic acid

(6) 2-Aminonaphthalene-3,6,8-trisulfonic acid

(7) Aniline-2,5-disulfonic acid

(8) Aniline

(9) m-Toluidine

(10) o-Anisidine

(11) Ammonia

(12) Ethylamine

(13) Ethanolamine

(14) β-alanine

(15) Taurine

(16) N-Methyltaurine

EXAMPLE 320

Example 318 was repeated, except that the amines described below wereused in place of the 1-aminobenzene-3-β-sulfatoethylsulfone used inExample 318 in amounts equimolar thereto, thereby obtaining thecorresponding asymmetric dioxazine compounds. ##STR384##

EXAMPLE 321

Example 318 was repeated, except that the dioxazine compound of thefollowing formula in the free acid form, ##STR385## was used in place ofthe starting dioxazine compound used in Example 318 in an amountequimolar thereto, thereby obtaining a corresponding asymmetricdioxazine compound.

EXAMPLE 322

A mixture of 2-methoxy-4,6-dichloro-s-triazine (18 parts) and the samestarting dioxazine compound as used in Example 318 was allowed to reactat 30° to 50° C. and a pH ranging from 2 to 7, followed by being reactedwith 1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts). The saltingout of the reaction mixture gave an asymmetric dioxazine compound of thefollowing formula in the free acid form. ##STR386##

EXAMPLE 323

Example 322 was repeated, except that 2-ethoxy-4,6-dichloro-s-triazinewas used in place of the 2-methoxy-4,6-dichloro-s-triazine used inExample 322 in an amount equimolar thereto, thereby obtaining acorresponding dioxazine compound.

EXAMPLE 324

Example 322 was repeated, except that amines (1) to (16) described inExample 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 322 in amountsequimolar thereto, thereby obtaining the corresponding asymmetricdioxazine compounds.

EXAMPLE 325

The same starting dioxazine compound (54.5 parts) as in Example 318 wasdissolved in water (1500 parts), and cyanuric chloride (18.5 parts) wasadded thereto. The mixture was stirred to complete the reaction at 5° to30° C., while keeping the pH within a range of 3 to 7 using sodiumcarbonate. Thereafter, sodium chloride was added thereto, and crystalsproduced were separated on a filter. The cake was then dissolved inwater (1500 parts), and 1-aminobenzene-3-β-sulfatoethylsulfone (28.1parts) was added thereto. The mixture was stirred to complete thereaction at 10° to 50° C., while keeping the pH within a range of 2 to6, thereby obtaining a corresponding dioxazine compound. ##STR387##

EXAMPLE 326

Example 325 was repeated, except that the amines (1) to (16) describedin Example 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 325 in amountsequimolar thereto, thereby obtaining the corresponding asymmetricdioxazine compounds.

EXAMPLE 327

A mixture of the asymmetric dioxazine compound (93.8 parts) which hadbeen obtained in Example 325, and 1-aminobenzene-3-β-sulfatoethylsulfone(28.1 parts) in water (1500 parts) was stirred to complete the reactionat 40° to 90° C., while keeping the pH within a range of 2 to 6, therebyobtaining an asymmetric dioxazine compound of the following formula inthe free acid form. ##STR388##

EXAMPLE 328

Example 327 was repeated, except that the amines (1) to (16) describedin Example 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 327 in amountsequimolar thereto, thereby obtaining the corresponding asymmetricdioxazine compounds.

EXAMPLE 329

Each of the asymmetric dioxazine compound obtained in Examples 318 to328 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a blue colorsuperior in fastness properties, particularly chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 330

A mixture of an intermediate dioxazine (83 parts) obtained in the samemanner as in Example 318 and ethylenechlorohydrin (41 parts) in water(1000 parts) was stirred to complete the reaction at 60° to 90° C. whilekeeping the pH within a range of 6 to 9 using aqueous sodium hydroxidesolution. Thereafter, potassium chloride was added to the reactionmixture, and the separation of the crystals produced gave anintermediate dioxazine compound of the following formula in the freeacid form. ##STR389##

A mixture of the above intermediate dioxazine compound (87.4 parts) and1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) in water (1000parts) was stirred to complete the reaction at 50° to 80° C. whilekeeping the pH within a range of 2 to 5. Potassium chloride was added tothe reaction mixture, and the separation of the crystals produced gavean asymmetric dioxazine compound of the following formula in the freeacid form. ##STR390##

EXAMPLE 331

1,4-phenylenediamine-2-sulfonic acid (18.8 parts) and2-aminoethyl-5-aminobenzenesulfonic acid (21.6 parts) were dissolved inwater (1000 parts) and adjusted to a pH ranging from 5 to 7. Thereafter,chloranil (24.6 parts) was added thereto, and the mixture was stirred tocomplete the reaction at 15° to 30° C., while keeping the pH within arange of 5 to 8 using aqueous sodium carbonate solution. Thereafter,sodium chloride was added to the reaction mixture, and the crystalsproduced were separated on a filter and then dried at 80° C. to obtain adianilide compound of the following formula in the free acid form.##STR391##

The dianilide compound (57.7 parts) was added to oleum of 5 to 30%strength containing potassium iodide (1.7 parts), and the mixture wasstirred to complete the reaction at 5° to 25° C. Thereafter, thereaction mixture was poured into ice water to produce crystals, whichwere separated on a filter. The cake was dissolved in water (1500 parts)and adjusted to a pH ranging from 5 to 7, and sodium chloride was addedthereto. The crystals produced were collected on a filter to obtain adioxazine compound of the following formula in the free acid form.##STR392##

Aniline-2,5-disulfonic acid (25.3 parts) was added to water (100 parts),followed by the adjustment of the pH to 7, and cyanuric chloride (18.5parts) was added thereto. The mixture was stirred to complete thereaction at 15° to 30° C., while keeping the pH within a range of 5 to 7using aqueous sodium carbonate solution. The resulting reaction mixturewas added to a solution of the above dioxazine compound (57.3 parts) inwater (1500 parts), and the mixture was stirred to complete the reactionat 20° to 50° C., while keeping the pH within a range of 5 to 7 usingaqueous sodium carbonate solution. Sodium chloride was added thereto toproduce crystals, and the separation of the crystals gave anintermediate dioxazine compound of the following formula in the freeacid form. ##STR393##

A mixture of the intermediate dioxazine compound (93.8 parts) and1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) in water (1500parts) was stirred to complete the reaction, while keeping the pH withina range of 2 to 5. Sodium chloride was added to the reaction mixture,and the crystals were collected on a filter to obtain an asymmetricdioxazine compound of the following formula in the free acid form.##STR394##

EXAMPLE 332

A solution of 2-aminoethyl-5-aminobenzenesulfonic acid (43.2 parts) inwater (1000 parts) was adjusted to a pH ranging from 5 to 7, andchloranil (24.6 parts) was added thereto. The mixture was stirred tocomplete the reaction at 15° to 40° C., while keeping the pH within arange of 5 to 8 using aqueous sodium carbonate solution. Sodium chloridewas added to the reaction mixture, producing crystals, which were thencollected on a filter and dried at 80° C. The product obtained was foundto be a dianilide having the following formula. ##STR395##

The dianilide (60.5 parts) was added to oleum of 5 to30% strength (1800parts) containing potassium iodide (1.7 parts), and the mixture wasstirred to complete the reaction at 5° to 25° C. Thereafter the reactionmixture was poured into ice water to produce crystals, which were thencollected on a filter. The cake was placed in water (1500 parts) andthen adjusted to a pH ranging from 5 to 7 with aqueous sodium hydroxidesolution. Salting out with sodium chloride gave a product, which wasfound to be the same dioxazine compound as that obtained in Example 331(λmax 615 nm). Using the dioxazine compound, Example 321 was repeated toobtain an asymmetric dioxazine compound, which was the same as thatobtained in Example 321.

EXAMPLE 333

Each of the asymmetric dioxazine compounds obtained in Examples 330 and331 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a blue colorsuperior in fastness properties, particularly chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 334

Example 330 was repeated, except that there each of the intermediatedioxazine compounds which had been prepared using amine compounds (1) to(16) described in Example 319 were used in place of the sulfanilic acidused in Example 318, thereby obtaining corresponding asymmetricdioxazine compounds.

EXAMPLE 335

Example 330 was repeated, except that amines (1) to (16) described inExample 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in that Example, therebyobtaining corresponding asymmetric dioxazine compounds.

EXAMPLE 336

Example 331 was repeated, except that amine compounds (1) to (16)described in Example 319 were used in place of theaniline-2,5-disulfonic acid used in Example 331, thereby obtainingcorresponding asymmetric dioxazine compounds.

EXAMPLE 337

Example 331 was repeated, except that amines (1) to (16) described inExample 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in that Example, therebyobtaining corresponding asymmetric dioxazine compounds.

EXAMPLE 338

Using a dioxazine compound having the formula described below in placeof the dioxazine compound used in Example 318, a process similar to thatin Example 318 or 330 was repeated to obtain a corresponding asymmetricdioxazine compound. ##STR396##

EXAMPLE 339

Example 331 was repeated, except that bromanil was used in place of thechloranil used in that Example, thereby obtaining a correspondingasymmetric dioxazine compound.

EXAMPLE 340

Example 332 was repeated, except that bromanil was used in place of thechloranil used in that Example, thereby obtaining a correspondingasymmetric dioxazine compound.

EXAMPLE 341

Each of the asymmetric dioxazine compounds obtained in Examples 334 to340 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a blue colorsuperior in fastness properties, particularly chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 342

2-Methoxy-4,6-dichloro-s-triazine (18 parts) and the dioxazine compound(57.3 parts) which had been prepared in Example 331 were allowed toreact at 30° to 50° C. and a pH ranging from 2 to 7, followed byreacting with 1-aminobenzene-3-β-sulfatoethylsulfone. The salting out ofthe reaction mixture gave an asymmetric dioxazine compound of thefollowing formula in the free acid form. ##STR397##

EXAMPLE 343

Example 342 was repeated, except that 2-ethoxy-4,6-dichloro-s-triazinewas used in place of the 2-methoxy-4,6-dichloro-s-triazine used inExample 342 in an amount equimolar thereto, thereby obtaining acorresponding asymmetric dioxazine compound.

EXAMPLE 344

Example 342 was repeated, except that amines (1) to (16) described inExample 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 342 in amountsequimolar thereto, thereby obtaining the corresponding asymmetricdioxazine compounds.

EXAMPLE 345

The dioxazine compound (57.3 parts) which had been prepared in Example331 was dissolved in water (1500 parts), and cyanuric chloride (18.5parts) was added thereto. The mixture was stirred to complete thereaction at 5° to 30° C., while keeping the pH within a range of 3 to 7with aqueous sodium carbonate solution.1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) was then addedthereto. The reaction was continued at 10° to 50° C. and a pH rangingfrom 2 to 6 to obtain an asymmetric dioxazine compound of the followingformula in the free acid form. ##STR398##

EXAMPLE 346

Example 345 was repeated, except that amines (1) to (16) described inExample 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 345, therebyobtaining a corresponding asymmetric dioxazine compound.

EXAMPLE 347

The asymmetric dioxazine compound (96.6 parts) which had been producedExample 345 was dissolved in water (1500 parts), and1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) was added thereto.The reaction was continued at 40° to 90° C., while keeping the pH withina range of 2 to 9 using aqueous sodium carbonate solution, therebyobtaining an asymmetric dioxazine compound of the following formula inthe free acid form. ##STR399##

EXAMPLE 348

Example 347 was repeated, except that amines (1) to (16) discribed inExample 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 347, therebyobtaining a corresponding asymmetric dioxazine compound.

EXAMPLE 349

Each of the asymmetric dioxazine compounds obtained in Examples 342 to348 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of a blue colorsuperior in fastness properties, particularly chlorine fastness. Thedioxazine compounds were also found to be superior in build-upproperties.

EXAMPLE 350

Using the asymmetric dioxazine compounds used in Examples 329, 333, 341and 349, color pastes having the following composition were prepared.

    ______________________________________                                        Asymmetric dioxazine compound                                                                           5 parts                                             Urea                      5 parts                                             Sodium alginate (5%) stock paste                                                                       50 parts                                             Hot water                25 parts                                             Sodium hydrogencarbonate  2 parts                                             Balance (water)          13 parts                                             ______________________________________                                    

Mercerized cotton broad cloths were printed with the color pastes havingthe above composition, pre-dried and steamed at 100° C. for 5 minutes.The treated cloths were washed with hot water, soaped, again washed withhot water and then dried. Thus, printed products of a blue colorexcellent in fastness properties, particularly chlorine fastness wereobtained.

EXAMPLES 351 TO 362

Using the amine compounds described below in place of the2-aminoethyl-5-aminobenzenesulfonic acid used in Example 331, Example331 was repeated to obtain the corresponding asymmetric dioxazinecompounds.

    ______________________________________                                        Exp.                                                                          No.         Amine compound                                                    ______________________________________                                        351                                                                                        ##STR400##                                                       352                                                                                        ##STR401##                                                       353                                                                                        ##STR402##                                                       354                                                                                        ##STR403##                                                       355                                                                                        ##STR404##                                                       356                                                                                        ##STR405##                                                       357                                                                                        ##STR406##                                                       358                                                                                        ##STR407##                                                       359                                                                                        ##STR408##                                                       360                                                                                        ##STR409##                                                       361                                                                                        ##STR410##                                                       362                                                                                        ##STR411##                                                       ______________________________________                                    

EXAMPLE 363

Example 318 was repeated, except that aniline-2,5-disulfonic acid wasused in place of the sulfanilic acid used therein. The asymmetricdioxazine compound obtained was subjected to sulfomethylation in a usualmanner. The product obtained was found to be the same as the asymmetricdioxazine compound obtained in Example 351.

EXAMPLE 364

Using aniline-2,5-disulfonic acid in place of the sulfanilic acid usedin Example 318, Example 318 was repeated to prepare a correspondingintermediate dioxazine compound. The intermediate was subjected tohydroxyethylation using ethylene oxide, followed by sulfuricacid-esterification in a conventional manner. The product obtained wasfound to be the same as the asymmetric dioxazine compound obtained inExample 352.

EXAMPLE 365

Example 318 was repeated, except that aniline-2,5-disulfonic acid wasused in place of the sulfanilic acid used therein. The correspondingasymmetric dioxazine compound obtained was subjected to methylolation ina usual manner, followed by esterification with sulfuric acid. Theproduct obtained was found to be the same as the asymmetric dioxazinecompound obtained in Example 354.

EXAMPLE 366

Each of Examples 351 to 362 were repeated, except that amine compounds(1) to (16) described in Example 319 were used in place of theaniline-2,5-disulfonic acid used therein, thereby obtainingcorresponding asymmetric dioxazine compounds.

EXAMPLE 367

Each of Examples 351 to 362 were repeated, except that amines (1) to(16) described in Example 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used therein, thereby obtainingcorresponding asymmetric dioxazine compounds.

EXAMPLE 368

Each of Examples 315 to 362 were repeated, except that bromanil was usedin place of the chloranil used therein in amounts equimolar thereto,thereby obtaining corresponding asymmetric dioxazine compounds.

EXAMPLE 369

Each of the asymmetric dioxazine compounds obtained in Examples 351 to362 and Examples 366 to 368 (each of 0.1, 0.3 and 0.6 parts) weredissolved in water (200 parts), and sodium sulfate (10 parts) and cotton(10 parts) were added thereto. The baths were heated to 60° C. and thensodium carbonate (4 parts) was added thereto. Thereafter, dyeing wascontinued for 1 hour at 60° C. The cotton taken out was washed withwater, soaped, again washed with water and then dried to obtain dyedproducts of a blue color superior in fastness properties, particularlychlorine fastness. The dioxazine compounds were also found to besuperior in build-up properties.

EXAMPLE 370

The asymmetric dioxazine compound which had been prepared in Example 322was subjected to sulfomethylation in a usual manner, thereby obtainingan asymmetric dioxazine compound of the following formula in the freeacid form. ##STR412##

EXAMPLE 371

Using 2-ethoxy-4,6-dichloro-s-triazine in place of the2-methoxy-4,6-dichloro-s-triazine used in Example 322, the procedure ofany of Examples 322 and 370 was repeated to obtain correspondingsulfomethylated asymmetric dioxazine compounds.

EXAMPLE 372

Using amines (1) to (16) described in Example 320 in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 322, procedure ofany of Examples 322 and 370 were repeated to obtain a correspondingsulfomethylated asymmetric dioxazine compounds.

EXAMPLE 373

The asymmetric dioxazine compound which had been prepared in Example 325was subjected to sulfomethylation in a usual manner, thereby obtainingan asymmetric dioxazine compound of the following formula in the freeacid form. ##STR413##

EXAMPLE 374

Using amines (1) to (16) described in Example 320 in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 325, theprocedure of any of Examples 325 and 373 were repeated to producecorresponding sulfomethylated asymmetric dioxazine compounds.

EXAMPLE 375

The asymmetric dioxazine compound (103.2 parts) which had been preparedin Example 373 was dissolved in water (1500 parts), and1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts) was added to thesolution. The reaction was continued at 40° to 90° C. while keeping thepH within a range of 2 to 6 with aqueous sodium carbonate solution,thereby obtaining an asymmetric dioxazine compound of the followingformula in the free acid form. ##STR414##

EXAMPLE 376

Example 375 was repeated, except that amines (1) to (16) described inExample 320 were used in place of the1-aminobenzene-3-β-sulfatoethylsulfone used in Example 375, therebyobtaining corresponding asymmetric dioxazine compounds.

EXAMPLE 377

The asymmetric dioxazine compound which had been prepared in Example 327was subjected to sulfomethylation in a usual manner. The productobtained was found to be the same as the asymmetric dioxazine compoundobtained in Example 375.

EXAMPLE 378

Each of the asymmetric dioxazine compounds obtained in Examples 370 to376 (each of 0.1, 0.3 and 0.6 parts) were dissolved in water (200parts), and sodium sulfate (10 parts) and cotton (10 parts) were addedthereto. The baths were heated to 60° C. and then sodium carbonate (4parts) was added thereto. Thereafter, dyeing was continued for 1 hour at60° C. The cotton taken out was washed with water, soaped, again washedwith water and then dried to obtain dyed products of blue color superiorin fastness properties, particularly chlorine fastness. The dioxazinecompounds also were found to be superior in build-up properties.

EXAMPLE 379

Using the asymmetric dioxazine compounds used in Examples 369 and 378,color pastes having the following composition were prepared.

    ______________________________________                                        Asymmetric dioxazine compound                                                                           5 parts                                             Urea                      5 parts                                             Sodium alginate (5%) stock paste                                                                       50 parts                                             Hot water                25 parts                                             Sodium hydrogencarbonate  2 parts                                             Balance (water)          13 parts                                             ______________________________________                                    

Mercerized cotton broad cloths were printed with the color pastes havingthe above composition, pre-dried and steamed at 100° C. for 5 minutes.The treated cloths were washed with hot water, soaped, again washed withhot water and then dried. Thus, printed products of a blue colorexcellent in fastness properties, particularly chlorine fastness wereobtained.

We claim:
 1. A compound represented by the following formula in the freeacid form, ##STR415## wherein R is halogen, sulfo or C₁ to C₄ alkoxy;R₁, R₂ and R₃ independently of one another are each hydrogen or C₁ to C₄alkyl which is unsubstituted or substituted by hydroxy, cyano, C₁ to C₄alkoxy, halogen, carbamoyl, carboxy, C₁ to C₄ alkoxycarbonyl, C₁ to C₄alkylcarbonyloxy, sulfo or sulfamoyl;X₁ and X₂ independently of oneanother are each hydrogen, halogen, alkyl, alkoxy or phenoxy; Y is--CH₂)₂, --CH₂)₃, --CH₂)₂ O--CH₂)₂, phenylene which is unsubstituted orsubstituted once or twice by methyl, ethyl, methoxy, ethoxy, chlorine,bromine, nitro, carboxy or sulfo, or naphthylene which is unsubstitutedor substituted once by sulfo; Z is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z' inwhich Z' is a group capable of being split by the action of an alkali; Vis hydrogen, alkyl which is unsubstituted or substituted by hydroxy,sulfo, sulfato, hydroxycarbonyloxy or carboxy, or an acyl group offormula (1),

    --W--R.sub.4                                               ( 1)

in which W is carbonyl or sulfonyl, and R₄ is alkyl which isunsubstituted or substituted by carboxy or sulfo, or phenyl which isunsubstituted or substituted by carboxy or sulfo; and Q is halogen,alkoxy, amino which is unsubstituted or substituted by alkyl,cycloalkyl, aralkyl, aryl or a heterocyclic ring selected from the groupconsisting of furan, thiophene, pyrazole, pyridine, pyrimidine,quinoline, benzimidazole, benzothiazole and benzoxazole, or aN-heterocyclic ring-constituting amino selected from the groupconsisting of morpholino, piperidino and piperazino, said alkyl,cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclicring-constituting amino each being unsubstituted or substituted byhalogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ to C₄alkyl, C₁ to C₄ alkoxy, ureido, hydroxy, carboxy, sulfomethyl or sulfo,or a group of formula (3), ##STR416## in which R₅ is hydrogen or C₁ toC₄ alkyl which is unsubstituted or substituted by hydroxy, cyano, C₁ toC₄ alkoxy, halogen, carbamoyl, carboxy, C₁ to C₄ alkoxycarbonyl, C₁ toC₄ alkylcarbonyloxy, sulfo or sulfamoyl, Y₁ is --CH₂)₂, --CH₂)₃, --CH₂)₂O--CH₂)₂, phenylene which is unsubstituted or substituted once or twiceby methyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro, carboxy orsulfo, or naphthylene which is unsubstituted or substituted once bysulfo, and Z₁ is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z" in which Z" is a groupcapable of being split by the action of an alkali.
 2. The compoundaccording to claim 1, wherein R₁ is hydrogen.
 3. The compound accordingto claim 1, wherein both X₁ and X₂ are chlorine or bromine.
 4. Thecompound according to claim 1, wherein Y is phenylene unsubstituted orsubstituted once or twice by methyl, ethyl, methoxy, ethoxy, chlorine,bromine, nitro, sulfo or carboxy, or naphthylene unsubstituted orsubstituted by sulfo.
 5. The compound according to claim 1, wherein R issulfo.
 6. A compound represented by the following formula in the freeacid form, ##STR417## wherein R₁, R₂ and R₃ independently of one anotherare each hydrogen or C₁ to C₄ alkyl which is unsubstituted orsubstituted by hydroxy, cyano, C₁ to C₄ alkoxy, halogen, carbamoyl,carboxy, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkylcarbonyloxy, sulfo orsulfamoyl;X₁ and X₂ independently of one another are each hydrogen,halogen, alkyl, alkoxy or phenoxy; Y is --CH₂)₂, --CH₂)₃, --CH₂)₂O--CH₂)₂, phenylene which is unsubstituted or substituted once or twiceby methyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro, carboxy orsulfo, or naphthylene which is unsubstituted or substituted once bysulfo; Z is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z' in which Z' is a groupcapable of being split by the action of an alkali; Q₁ and Q₂independently of one another are each amino which is unsubstituted orsubstituted by alkyl, cycloalkyl, aralkyl, aryl or a heterocyclic ringselected from the group consisting of furan, thiophene, pyrazole,pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole andbenzoxazole, or an N-heterocyclic ring-constituting amino selected fromthe group consisting of morpholino, piperidino and piperazino, saidalkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclicring-constituting amino each being unsubstituted or substituted byhalogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ to C₄alkyl, C₁ to C₄ alkoxy, ureido, hydroxy, carboxy, sulfomethyl or sulfo;and Q₃ is amino which is unsubstituted or substituted by alkyl,cycloalkyl, aralkyl, aryl or a heterocyclic ring selected from the groupconsisting of furan, thiophene, pyrazole, pyridine, pyrimidine,quinoline, benzimidazole, benzothiazole and benzoxazole, or anN-heterocyclic ring-constituting amino selected from the groupconsisting of morpholino, piperidino and piperazino, said alkyl,cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclicring-constituting amino each being unsubstituted or substituted byhalogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ to C₄alkyl, C₁ to C₄ alkoxy, ureido, hydroxy, carboxy, sulfomethyl or sulfoor a group of formula (3), ##STR418## in which R₅ is hydrogen or C₁ toC₄ alkyl which is unsubstituted or substituted by hydroxy, cyano, C₁ toC₄ alkoxy, halogen, carbamoyl, carboxy, C₁ to C₄ alkoxycarbonyl, C₁ toC₄ alkylcarbonyloxy, sulfo or sulfamoyl, Y₁ is --CH₂)₂, --CH₂)₃, --CH₂)₂O--CH₂)₂, phenylene which is unsubstituted or substituted once or twiceby methyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro, carboxy orsulfo, or naphthylene which is unsubstituted or substituted once bysulfo, and Z₁ is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z" in which Z" is a groupcapable of being split by the action of an alkali.
 7. The compoundaccording to claim 6, wherein both R₁ and R₃ are hydrogen.
 8. A compoundrepresented by the following formula in the free acid form, ##STR419##wherein R₁, R₂ and R₃ independently of one another are each hydrogen orC₁ to C₄ alkyl which is unsubstituted or substituted by hydroxy, cyano,C₁ to C₄ alkoxy, halogen, carbamoyl, carboxy, C₁ to C₄ alkoxycarbonyl,C₁ to C₄ alkylcarbonyloxy, sulfo or sulfamoyl;X₁ and X₂ independently ofone another are each hydrogen, halogen, alkyl, alkoxy or phenoxy; Y is--CH₂)₂, --CH₂)₃, --CH₂)₂ O--CH₂)₂, phenylene which is unsubstituted orsubstituted once or twice by methyl, ethyl, methoxy, ethoxy, chlorine,bromine, nitro, carboxy or sulfo, or naphthylene which is unsubstitutedor substituted once by sulfo; Z is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z' inwhich Z' is a group capable of being split by the action of an alkali; Wis carbonyl or sulfonyl; R₄ is alkyl which is unsubstituted orsubstituted by carboxy or sulfo, or phenyl which is unsubstituted orsubstituted by carboxy or sulfo; and Q₃ is amino which is unsubstitutedor substituted by alkyl, cycloalkyl, aralkyl, aryl or a heterocyclicring selected from the group consisting of furan, thiophene, pyrazole,pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole andbenzoxazole, or an N-heterocyclic ring-constituting amino selected fromthe group consisting of morpholino, piperidino and piperazino, saidalkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclicring-constituting amino each being unsubstituted or substituted byhalogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ to C₄alkyl, C₁ to C₄ alkoxy, ureido, hydroxy, carboxy, sulfomethyl or sulfo,or a group of formula (3), ##STR420## in which R₅ is hydrogen or C₁ toC₄ alkyl which is unsubstituted or substituted by hydroxy, cyano, C₁ toC₄ alkoxy, halogen, carbamoyl, carboxy, C₁ to C₄ alkoxycarbonyl, C₁ toC₄ alkylcarbonyloxy, sulfo or sulfamoyl, Y₁ is --CH₂)₂, --CH₂)₃, --CH₂)₂O--CH₂)₂, phenylene which is unsubstituted or substituted once or twiceby methyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro, carboxy orsulfo, or naphthylene which is unsubstituted or substituted once bysulfo, and Z₁ is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z" in which Z" is a groupcapable of being split by the action of an alkali.
 9. The compoundaccording to claim 8, wherein both R₁ and R₃ are hydrogen.
 10. Acompound represented by the following formula in the free acid form,##STR421## wherein R₁, R₂ and R₃ independently of one another are eachhydrogen or C₁ to C₄ alkyl which is unsubstituted or substituted byhydroxy, cyano, C₁ to C₄ alkoxy, halogen, carbamoyl, carboxy, C₁ to C₄alkoxycarbonyl, C₁ to C₄ alkylcarbonyloxy, sulfo or sulfamoyl;X₁ and X₂independently of one another are each hydrogen, halogen, alkyl, alkoxyor phenoxy; Y is --CH₂)₂, --CH₂)₃, --CH₂)₂ O--CH₂)₂, phenylene which isunsubstituted or substituted once or twice by methyl, ethyl, methoxy,ethoxy, chlorine, bromine, nitro, carboxy or sulfo, or naphthylene whichis unsubstituted or substituted once by sulfo; Z is --SO₂ CH═CH₂ or--SO₂ CH₂ CH₂ Z' in which Z' is a group capable of being split by theaction of an alkali; Q is halogen, alkoxy, amino which is unsubstitutedor substituted by alkyl, cycloalkyl, aralkyl, aryl or a heterocyclicring selected from the group consisting of furan, thiophene, pyrazole,pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole andbenzoxazole, or an N-heterocyclic ring-constituting amino selected fromthe group consisting of morpholino, piperidino and piperazino, saidalkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclicring-constituting amino each being unsubstituted or substituted byhalogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ to C₄alkyl, C₁ to C₄ alkoxy, ureido, hydroxy, carboxy, sulfomethyl or sulfo,or a group of formula (3), ##STR422## in which R₅ is hydrogen or C₁ toC₄ alkyl which is unsubstituted or substituted by hydroxy, cyano, C₁ toC₄ alkoxy, halogen, carbamoyl, carboxy, C₁ to C₄ alkoxycarbonyl, C₁ toC₄ alkylcarbonyloxy, sulfo or sulfamoyl, Y₁ is --CH₂)₂, --CH₂)₃, --CH₂)₂O--CH₂)₂, phenylene which is unsubstituted or substituted once or twiceby methyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro, carboxy orsulfo, or naphthylene which is unsubstituted or substituted once bysulfo, and Z₁ is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Z" in which Z" is a groupcapable of being split by the action of an alkali; and R₆ is C₁ to C₄sulfoalkyl.
 11. The compound according to claim 6, wherein R₁ ishydrogen.
 12. The compound according to claim 6, wherein both X₁ and X₂are chlorine or bromine.
 13. The compound according to claim 6, whereinY is phenylene which is unsubstituted or substituted once or twice bymethyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro, sulfo orcarboxy, or naphthylene unsubstituted or substituted by sulfo.
 14. Thecompound according to claim 8, wherein R₁ is hydrogen.
 15. The compoundaccording to claim 8, wherein both X₁ and X₂ are chlorine or bromine.16. The compound according to claim 8, wherein Y is phenylene which isunsubstituted or substituted once or twice by methyl, ethyl, methoxy,ethoxy, chlorine, bromine, nitro, sulfo or carboxy, or naphthyleneunsubstituted or substituted by sulfo.
 17. The compound according toclaim 10, wherein R₁ is hydrogen.
 18. The compound according to claim10, wherein both X₁ and X₂ are chlorine or bromine.
 19. The compoundaccording to claim 10, wherein Y is phenylene which is unsubstituted orsubstituted once or twice by methyl, ethyl, methoxy, ethoxy, chlorine,bromine, nitro, sulfo or carboxy, or naphthylene unsubstituted orsubstituted by sulfo.